Security features incorporating photoluminescent phosphor powders and methods for making security features

ABSTRACT

Photoluminescent phosphor powders and a method for making phosphor powders. The phosphor powders have a small particle size, narrow particle size distribution and are substantially spherical. The method of the invention advantageously permits the economic production of such powders. The invention also relates to improved devices, such as display devices and lighting elements, incorporating the phosphor powders.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. patent applicationSer. No. 10/730,756, filed Dec. 8, 2003, now U.S. Pat. No. 7,229,572,which is a divisional application of U.S. patent application Ser. No.09/800,426 filed on Mar. 6, 2001, now U.S. Pat. No. 6,660,185, which isa divisional application of U.S. patent application Ser. No. 09/141,393filed on Aug. 27, 1998, now U.S. Pat. No. 6,197,218, which is acontinuation-in-part application of U.S. patent application Ser. No.09/028,603, now U.S. Pat. No. 6,180,029, Ser. No. 09/030,060, now U.S.Pat. No. 6,153,123 and Ser. No. 09/030,057, now U.S. Pat. No. 6,338,809,each filed Feb. 24, 1998, and claiming priority to U.S. ProvisionalApplication Nos. 60/038,262 and 60/039,450, each filed on Feb. 24, 1997.Each of the foregoing is incorporated herein by reference in itsentirety.

STATEMENT REGARDING FEDERALLY-SPONSORED RESEARCH/DEVELOPMENT

This invention was made with Government support under contractsN00014-95-C-0278 and N00014-96-C-0395 awarded by the Office of NavalResearch. The Government has certain rights in the invention.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to photoluminescent phosphor powders,methods for producing photoluminescent phosphor powders and devices suchas flat panel displays and lighting elements incorporating the powders.In particular, the present invention is directed to photoluminescentphosphor powders having well-controlled chemical and physicalproperties. The present invention also relates to a method for producingsuch powders by spray-conversion.

2. Description of Related Art

Phosphors are compounds that are capable of emitting useful quantitiesof radiation in the visible and/or ultraviolet spectrums upon excitationof the material by an external energy source. Due to this property,phosphor compounds have long been utilized in cathode ray tube (CRT)screens for televisions and similar devices. Typically, inorganicphosphor compounds include a host material doped with a small amount ofan activator ion. Phosphor powders, particularly photoluminescentphosphor powders, are used in fluorescent lighting elements includingcommon industrial lights and backlights for display screens.

More recently, phosphor powders have been utilized in many advanceddisplay devices that provide illuminated text, graphics or video output,including flat panel display devices such as plasma displays. Plasmadisplay panels utilize a gas trapped between transparent layers thatemits ultraviolet light when excited by an electric field. Theultraviolet light stimulates phosphors on the screen to emit visiblelight. Plasma displays are particularly useful for larger displays, suchas greater than about 20 diagonal inches.

In addition, photoluminescent phosphor powders can also be used as ameans of identifying an article of manufacture, such as a confidentialdocument, currency, postage, and the like.

There are a number of requirements for phosphor powders, which can varydependent upon the specific application of the powder. Generally,phosphor powders should have one or more of the following properties:high purity; high crystallinity; small particle size; narrow particlesize distribution; spherical morphology; controlled surface chemistry;homogenous distribution of the activator ion; good dispersibility; andlow porosity. The proper combination of the foregoing properties willresult in a phosphor powder with high luminescent intensity and longlifetime that can be used in many applications. It is also advantageousfor many applications to provide phosphor powders that are surfacepassivated or coated, such as with a thin, uniform dielectric orsemiconducting coating.

Numerous methods have been proposed for producing phosphor particles.One such method is referred to as the solid-state method. In thisprocess, the phosphor precursor materials are mixed in the solid stateand are heated so that the precursors react and form a powder of thephosphor material. For example, U.S. Pat. No. 4,925,703 by Kasenga etal. discloses a method for the production of a manganese activated zincsilicate phosphor (ZnSiO₄:Mn). The method includes a step of dryblending a mixture of starting components such as zinc oxide, silicicacid and manganese carbonate and firing the blended mixture at about1250° C. The resulting phosphor is broken up or crushed into smallerparticles. Solid-state routes, and many other production methods,utilize such a grinding step to reduce the particle size of the powders.The mechanical grinding damages the surface of the phosphor, formingdead layers which inhibit the brightness of the phosphor powders.

Phosphor powders have also been made by liquid precipitation. In thesemethods, a solution which includes phosphor particle precursors ischemically treated to precipitate phosphor particles or phosphorparticle precursors. These particles are typically calcined at anelevated temperature to produce the phosphor compound. The particlesmust often be further crushed, as is the case with solid-state methods.

In yet another method, phosphor particle precursors or phosphorparticles are dispersed in a solution which is then spray dried toevaporate the liquid. The phosphor particles are thereafter sintered inthe solid state at an elevated temperature to crystallize the powder andform a phosphor. For example, U.S. Pat. No. 4,948,527 by Ritsko et al.discloses a process for producing Y₂O₃:Eu phosphors by dispersingyttrium oxide in a europium citrate solution to form a slurry which isthen spray dried. The spray dried powder was then converted to an oxideby firing at about 1000° C. for two hours and then at 1600° C for aboutfour hours. The fired powder was then lightly crushed and cleaned torecover useful phosphor particles.

U.S. Pat. No. 5,644,193 by Matsuda et al. discloses phosphor powdershaving an average particle size of up to 20 μm. The phosphors caninclude rare earth oxides, rare earth oxysulfides and tungstates. Theparticles are produced by fusing phosphor particles in a thermal plasmaand rapidly cooling the particles.

Despite the foregoing, there remains a need for photoluminescentphosphor powders with high luminescent intensity that include particleshaving a substantially spherical morphology, narrow particle sizedistribution, a high degree of crystallinity and good homogeneity. Thepowder should have good dispersibility and the ability to be fabricatedinto thin layers having uniform thickness. Phosphor powders having theseproperties will be particularly useful in flat panel displays, such asplasma display panels.

SUMMARY OF THE INVENTION

The present invention provides improved phosphor powder batchesincluding phosphors having a small particle size, narrow particle sizedistribution, spherical morphology and good crystallinity. The presentinvention also provides methods for forming phosphor powder batches anddevices, such as flat panel displays and fluorescent lighting elementsincorporating the powder batches.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a process block diagram showing one embodiment of the processof the present invention.

FIG. 2 is a side view in cross section of one embodiment of aerosolgenerator of the present invention.

FIG. 3 is a top view of a transducer mounting plate showing a 49transducer array for use in an aerosol generator of the presentinvention.

FIG. 4 is a top view of a transducer mounting plate for a 400 transducerarray for use in an ultrasonic generator of the present invention.

FIG. 5 is a side view of the transducer mounting plate shown in FIG. 4.

FIG. 6 is a partial side view showing the profile of a single transducermounting receptacle of the transducer mounting plate shown in FIG. 4.

FIG. 7 is a partial side view in cross-section showing an alternativeembodiment for mounting an ultrasonic transducer.

FIG. 8 is a top view of a bottom retaining plate for retaining aseparator for use in an aerosol generator of the present invention.

FIG. 9 is a top view of a liquid feed box having a bottom retainingplate to assist in retaining a separator for use in an aerosol generatorof the present invention.

FIG. 10 is a side view of the liquid feed box shown in FIG. 9.

FIG. 11 is a side view of a gas tube for delivering gas within anaerosol generator of the present invention.

FIG. 12 shows a partial top view of gas tubes positioned in a liquidfeed box for distributing gas relative to ultrasonic transducerpositions for use in an aerosol generator of the present invention.

FIG. 13 shows one embodiment for a gas distribution configuration forthe aerosol generator of the present invention.

FIG. 14 shows another embodiment for a gas distribution configurationfor the aerosol generator of the present invention.

FIG. 15 is a top view of one embodiment of a gas distribution plate/gastube assembly of the aerosol generator of the present invention.

FIG. 16 is a side view of one embodiment of the gas distributionplate/gas tube assembly shown in FIG. 15.

FIG. 17 shows one embodiment for orienting a transducer in the aerosolgenerator of the present invention.

FIG. 18 is a top view of a gas manifold for distributing gas within anaerosol generator of the present invention.

FIG. 19 is a side view of the gas manifold shown in FIG. 18.

FIG. 20 is a top view of a generator lid of a hood design for use in anaerosol generator of the present invention.

FIG. 21 is a side view of the generator lid shown in FIG. 20.

FIG. 22 is a process block diagram of one embodiment of the process ofthe present invention including a droplet classifier.

FIG. 23 is a top view in cross section of an impactor of the presentinvention for use in classifying an aerosol.

FIG. 24 is a front view of a flow control plate of the impactor shown inFIG. 23.

FIG. 25 is a front view of a mounting plate of the impactor shown inFIG. 23.

FIG. 26 is a front view of an impactor plate assembly of the impactorshown in FIG. 23.

FIG. 27 is a side view of the impactor plate assembly shown in FIG. 26.

FIG. 28 is a process block diagram of one embodiment of the presentinvention including a particle cooler.

FIG. 29 is a top view of a gas quench cooler of the present invention.

FIG. 30 is an end view of the gas quench cooler shown in FIG. 29.

FIG. 31 is a side view of a perforated conduit of the quench coolershown in FIG. 29.

FIG. 32 is a side view showing one embodiment of a gas quench cooler ofthe present invention connected with a cyclone.

FIG. 33 is a process block diagram of one embodiment of the presentinvention including a particle coater.

FIG. 34 is a block diagram of one embodiment of the present inventionincluding a particle modifier.

FIG. 35 shows cross sections of various particle morphologies of somecomposite particles manufacturable according to the present invention.

FIG. 36 is a block diagram of one embodiment of the process of thepresent invention including the addition of a dry gas between theaerosol generator and the furnace.

FIG. 37 schematically illustrates a plasma display panel according to anembodiment of the present invention.

FIG. 38 illustrates pixel regions on a display device according to theprior art.

FIG. 39 illustrates pixel regions on a display device according to anembodiment of the present invention.

FIG. 40 schematically illustrates a fluorescent lighting elementaccording to an embodiment of the present invention.

FIG. 41 schematically illustrates a phosphor powder layer dispersed on alighting element tube according to an embodiment of the presentinvention.

FIG. 42 illustrates an SEM photomicrograph of a photoluminescent powderbatch according to an embodiment of the present invention.

FIG. 43 illustrates the particle size distribution of a photoluminescentpowder batch according to an embodiment of the present invention.

FIG. 44 illustrates an SEM photomicrograph of a photoluminescent powderbatch according to an embodiment of the present invention.

FIG. 45 illustrates the particle size distribution of a photoluminescentpowder batch according to an embodiment of the present invention.

FIG. 46 illustrates an x-ray diffraction pattern of a photoluminescentpowder batch according to an embodiment of the present invention.

FIG. 47 illustrates an SEM photomicrograph of a photoluminescent powderbatch according to an embodiment of the present invention.

FIG. 48 illustrates the particle size distribution of a photoluminescentpowder batch according to an embodiment of the present invention.

FIG. 49 illustrates an x-ray diffraction pattern of a photoluminescentpowder batch according to an embodiment of the present invention.

FIG. 50 illustrates an SEM photomicrograph of a photoluminescent powderbatch according to an embodiment of the present invention.

FIG. 51 illustrates the particle size distribution of a photoluminescentpowder batch according to an embodiment of the present invention.

FIG. 52 illustrates an x-ray diffraction pattern of a photoluminescentpowder batch according to an embodiment of the present invention.

DESCRIPTION OF THE INVENTION

The present invention is generally directed to photoluminescent phosphorpowders and methods for producing the powders, as well as devices whichincorporate the powders. Photoluminescent phosphors emit light uponstimulation by other light. The stimulating light usually has higherenergy than the emitted light. For example, a photoluminescent phosphorcan emit visible light when stimulated by ultraviolet light. Thesephosphors are utilized in plasma display panels and fluorescent lightingelements.

In one aspect, the present invention provides a method for preparing aparticulate product. A feed of liquid-containing, flowable medium,including at least one precursor for the desired particulate product, isconverted to aerosol form, with droplets of the medium being dispersedin and suspended by a carrier gas. Liquid from the droplets in theaerosol is then removed to permit formation in a dispersed state of thedesired particles. In one embodiment, the particles are subjected, whilestill in a dispersed state, to compositional or structural modification,if desired. Compositional modification may include, for example, coatingthe particles. Structural modification may include, for example,crystallization, recrystallization or morphological alteration of theparticles. The term powder is often used herein to refer to theparticulate product of the present invention. The use of the term powderdoes not indicate, however, that the particulate product must be dry orin any particular environment. Although the particulate product istypically manufactured in a dry state, the particulate product may,after manufacture, be placed in a wet environment, such as in a paste orslurry.

The process of the present invention is particularly well suited for theproduction of particulate products of finely divided particles having asmall weight average size. In addition to making particles within adesired range of weight average particle size, with the presentinvention the particles may be produced with a desirably narrow sizedistribution, thereby providing size uniformity that is desired for manyapplications.

In addition to control over particle size and size distribution, themethod of the present invention provides significant flexibility forproducing phosphor particles of varying composition, crystallinity andmorphology. For example, the present invention may be used to producehomogeneous particles involving only a single phase or multi-phaseparticles including multiple phases. In the case of multi-phaseparticles, the phases may be present in a variety of morphologies. Forexample, one phase may be uniformly dispersed throughout a matrix ofanother phase. Alternatively, one phase may form an interior core whileanother phase forms a coating that surrounds the core. Othermorphologies are also possible, as discussed more fully below.

Referring now to FIG. 1, one embodiment of the process of the presentinvention is described. A liquid feed 102, including at least oneprecursor for the desired particles, and a carrier gas 104 are fed to anaerosol generator 106 where an aerosol 108 is produced. The aerosol 108is then fed to a furnace 110 where liquid in the aerosol 108 is removedto produce particles 112 that are dispersed in and suspended by gasexiting the furnace 110. The particles 112 are then collected in aparticle collector 114 to produce a particulate product 116.

As used herein, the liquid feed 102 is a feed that includes one or moreflowable liquids as the major constituent(s), such that the feed is aflowable medium. The liquid feed 102 need not comprise only liquidconstituents. The liquid feed 102 may comprise only constituents in oneor more liquid phase, or it may also include particulate materialsuspended in a liquid phase. The liquid feed 102 must, however, becapable of being atomized to form droplets of sufficiently small sizefor preparation of the aerosol 108. Therefore, if the liquid feed 102includes suspended particles, those particles should be relatively smallin relation to the size of droplets in the aerosol 108. Such suspendedparticles should typically be smaller than about 1 μm in size,preferably smaller than about 0.5 μm in size, and more preferablysmaller than about 0.3 μm in size and most preferably smaller than about0.1 μm in size. Most preferably, the suspended particles should becolloidal. The suspended particles could be finely divided particles, orcould be agglomerate masses comprised of agglomerated smaller primaryparticles. For example, 0.5 μm particles could be agglomerates ofnanometer-sized primary particles. When the liquid feed 102 includessuspended particles, the particles typically comprise no greater thanabout 10 weight percent of the liquid feed.

As noted, the liquid feed 102 includes at least one precursor forpreparation of the particles 112. The precursor may be a substance ineither a liquid or solid phase of the liquid feed 102. Frequently, theprecursor will be a material, such as a salt, dissolved in a liquidsolvent of the liquid feed 102. The precursor may undergo one or morechemical reactions in the furnace 110 to assist in production of theparticles 112. Alternatively, the precursor material may contribute toformation of the particles 112 without undergoing chemical reaction.This could be the case, for example, when the liquid feed 102 includes,as a precursor material, suspended particles that are not chemicallymodified in the furnace 110. In any event, the particles 112 comprise atleast one component originally contributed by the precursor.

The liquid feed 102 may include multiple precursor materials, which maybe present together in a single phase or separately in multiple phases.For example, the liquid feed 102 may include multiple precursors insolution in a single liquid vehicle. Alternatively, one precursormaterial could be in a solid particulate phase and a second precursormaterial could be in a liquid phase. Also, one precursor material couldbe in one liquid phase and a second precursor material could be in asecond liquid phase, such as could be the case when the liquid feed 102comprises an emulsion. Different components contributed by differentprecursors may be present in the particles together in a single materialphase, or the different components may be present in different materialphases when the particles 112 are composites of multiple phases.Specific examples of preferred precursors for photoluminescent phosphorparticles are discussed more fully below.

The carrier gas 104 may comprise any gaseous medium in which dropletsproduced from the liquid feed 102 may be dispersed in aerosol form.Also, the carrier gas 104 may be inert, in that the carrier gas 104 doesnot participate in formation of the particles 112. Alternatively, thecarrier gas may have one or more active component(s) that contribute toformation of the particles 112. In that regard, the carrier gas mayinclude one or more reactive components that react in the furnace 110 tocontribute to formation of the particles 112. Preferred carrier gascompositions for photoluminescent phosphor particles are discussed morefully below.

The aerosol generator 106 atomizes the liquid feed 102 to form dropletsin a manner to permit the carrier gas 104 to sweep the droplets away toform the aerosol 108. The droplets comprise liquid from the liquid feed102. The droplets may, however, also include nonliquid material, such asone or more small particles held in the droplet by the liquid. Forexample, when the particles 112 are composite, or multi-phase,particles, one phase of the composite may be provided in the liquid feed102 in the form of suspended precursor particles and a second phase ofthe composite may be produced in the furnace 110 from one or moreprecursors in the liquid phase of the liquid feed 102. Furthermore theprecursor particles could be included in the liquid feed 102, andtherefore also in droplets of the aerosol 108, for the purpose only ofdispersing the particles for subsequent compositional or structuralmodification during or after processing in the furnace 110.

An important aspect of the present invention is generation of theaerosol 108 with droplets of a small average size, narrow sizedistribution. In this manner, the particles 112 may be produced at adesired small size with a narrow size distribution, which areadvantageous for many applications.

The aerosol generator 106 is capable of producing the aerosol 108 suchthat it includes droplets having a weight average size in a range havinga lower limit of about 1 μm and preferably about 2 μm; and an upperlimit of about 10 μm; preferably about 7 μm, more preferably about 5 μmand most preferably about 4 μm. A weight average droplet size in a rangeof from about 2 μm to about 4 μm is more preferred for mostapplications, with a weight average droplet size of about 3 μm beingparticularly preferred for some applications. The aerosol generator isalso capable of producing the aerosol 108 such that it includes dropletsin a narrow size distribution. Preferably, the droplets in the aerosolare such that at least about 70 percent (more preferably at least about80 weight percent and most preferably at least about 85 weight percent)of the droplets are smaller than about 10 pm and more preferably atleast about 70 weight percent (more preferably at least about 80 weightpercent and most preferably at least about 85 weight percent) aresmaller than about 5 μm. Furthermore, preferably no greater than about30 weight percent, more preferably no greater than about 25 weightpercent and most preferably no greater than about 20 weight percent, ofthe droplets in the aerosol 108 are larger than about twice the weightaverage droplet size.

Another important aspect of the present invention is that the aerosol108 may be generated without consuming excessive amounts of the carriergas 104. The aerosol generator 106 is capable of producing the aerosol108 such that it has a high loading, or high concentration, of theliquid feed 102 in droplet form. In that regard, the aerosol 108preferably includes greater than about 1×10⁶ droplets per cubiccentimeter of the aerosol 108, more preferably greater than about 5×10⁶droplets per cubic centimeter, still more preferably greater than about1×10⁷ droplets per cubic centimeter, and most preferably greater thanabout 5×10⁷ droplets per cubic centimeter. That the aerosol generator106 can produce such a heavily loaded aerosol 108 is particularlysurprising considering the high quality of the aerosol 108 with respectto small average droplet size and narrow droplet size distribution.Typically, droplet loading in the aerosol is such that the volumetricratio of liquid feed 102 to carrier gas 104 in the aerosol 108 is largerthan about 0.04 milliliters of liquid feed 102 per liter of carrier gas104 in the aerosol 108, preferably larger than about 0.083 millilitersof liquid feed 102 per liter of carrier gas 104 in the aerosol 108, morepreferably larger than about 0.167 milliliters of liquid feed 102 perliter of carrier gas 104, still more preferably larger than about 0.25milliliters of liquid feed 102 per liter of carrier gas 104, and mostpreferably larger than about 0.333 milliliters of liquid feed 102 perliter of carrier gas 104.

This capability of the aerosol generator 106 to produce a heavily loadedaerosol 108 is even more surprising given the high droplet output rateof which the aerosol generator 106 is capable, as discussed more fullybelow. It will be appreciated that the concentration of liquid feed 102in the aerosol 108 will depend upon the specific components andattributes of the liquid feed 102 and, particularly, the size of thedroplets in the aerosol 108. For example, when the average droplet sizeis from about 2 μm to about 4 μm, the droplet loading is preferablylarger than about 0.15 milliliters of aerosol feed 102 per liter ofcarrier gas 104, more preferably larger than about 0.2 milliliters ofliquid feed 102 per liter of carrier gas 104, even more preferablylarger than about 0.2 milliliters of liquid feed 102 per liter ofcarrier gas 104, and most preferably larger than about 0.3 millilitersof liquid feed 102 per liter of carrier gas 104. When reference is madeherein to liters of carrier gas 104, it refers to the volume that thecarrier gas 104 would occupy under conditions of standard temperatureand pressure.

The furnace 110 may be any suitable device for heating the aerosol 108to evaporate liquid from the droplets of the aerosol 108 and therebypermit formation of the particles 112. The maximum average streamtemperature, or conversion temperature, refers to the maximum averagetemperature that an aerosol stream attains while flowing through thefurnace. This is typically determined by a temperature probe insertedinto the furnace. Preferred conversion temperatures according to thepresent invention are discussed more fully below.

Although longer residence times are possible, for many applications,residence time in the heating zone of the furnace 110 of shorter thanabout 4 seconds is typical, with shorter than about 2 seconds beingpreferred, such as from about 1 to 2 seconds. The residence time shouldbe long enough, however, to assure that the particles 112 attain thedesired maximum stream temperature for a given heat transfer rate. Inthat regard, with extremely short residence times, higher furnacetemperatures could be used to increase the rate of heat transfer so longas the particles 112 attain a maximum temperature within the desiredstream temperature range. That mode of operation, however, is notpreferred. Also, it is preferred that, in most cases, the maximum streamtemperature not be attained in the furnace 110 until substantially atthe end of the heating zone in the furnace 110. For example, the heatingzone will often include a plurality of heating sections that are eachindependently controllable. The maximum stream temperature shouldtypically not be attained until the final heating section, and morepreferably until substantially at the end of the last heating section.This is important to reduce the potential for thermophoretic losses ofmaterial. Also, it is noted that as used herein, residence time refersto the actual time for a material to pass through the relevant processequipment. In the case of the furnace, this includes the effect ofincreasing velocity with gas expansion due to heating.

Typically, the furnace 110 will be a tube-shaped furnace, so that theaerosol 108 moving into and through the furnace does not encounter sharpedges on which droplets could collect. Loss of droplets to collection atsharp surfaces results in a lower yield of particles 112. Moreimportant, however, the accumulation of liquid at sharp edges can resultin re-release of undesirably large droplets back into the aerosol 108,which can cause contamination of the particulate product 116 withundesirably large particles. Also, overtime, such liquid collection atsharp surfaces can cause fouling of process equipment, impairing processperformance.

The furnace 110 may include a heating tube made of any suitablematerial. The tube material may be a ceramic material, for example,mullite, silica (quartz) or alumina. Alternatively, the tube may bemetallic. Advantages of using a metallic tube are low cost, ability towithstand steep temperature gradients and large thermal shocks,machinability and weldability, and ease of providing a seal between thetube and other process equipment. Disadvantages of using a metallic tubeinclude limited operating temperature and increased reactivity in somereaction systems. One type of tube that is particularly useful accordingto the present invention is a lined metallic tube, such as a metal tubewhose interior surface is lined with alumina.

When a metallic tube is used in the furnace 110, it is preferably a highnickel content stainless steel alloy, such as a 330 stainless steel, ora nickel-based super alloy. As noted, one of the major advantages ofusing a metallic tube is that the tube is relatively easy to seal withother process equipment. In that regard, flange fittings may be weldeddirectly to the tube for connecting with other process equipment.Metallic tubes are generally preferred for spray-converting particlesthat do not require a maximum tube wall temperature of higher than about1100° C. during particle manufacture, which is the case for thephotoluminescent phosphor particles according to the present invention.

Also, although the present invention is described with primary referenceto a furnace reactor, which is preferred, it should be recognized that,except as noted, any other thermal reactor, including a flame reactor ora plasma reactor, could be used instead. A furnace reactor is, however,preferred, because of the generally even heating characteristic of afurnace for attaining a uniform stream temperature.

The particle collector 114, may be any suitable apparatus for collectingparticles 112 to produce the particulate product 116. One preferredembodiment of the particle collector 114 uses one or more filter toseparate the particles 112 from gas. Such a filter may be of any type,including a bag filter. Another preferred embodiment of the particlecollector uses one or more cyclone to separate the particles 112. Otherapparatus that may be used in the particle collector 114 includes anelectrostatic precipitator. Also, collection should normally occur at atemperature above the condensation temperature of the gas stream inwhich the particles 112 are suspended. Also, collection should normallybe at a temperature that is low enough to prevent significantagglomeration of the particles 112.

Of significant importance to the operation of the process of the presentinvention is the aerosol generator 106, which must be capable ofproducing a high quality aerosol with high droplet loading, aspreviously noted. With reference to FIG. 2, one embodiment of an aerosolgenerator 106 of the present invention is described. The aerosolgenerator 106 includes a plurality of ultrasonic transducer discs 120that are each mounted in a transducer housing 122. The transducerhousings 122 are mounted to a transducer mounting plate 124, creating anarray of the ultrasonic transducer discs 120. Any convenient spacing maybe used for the ultrasonic transducer discs 120. Center-to-centerspacing of the ultrasonic transducer discs 120 of about 4 centimeters isoften adequate. The aerosol generator 106, as shown in FIG. 2, includesforty-nine transducers in a 7×7 array. The array configuration is asshown in FIG. 3, which depicts the locations of the transducer housings122 mounted to the transducer mounting plate 124.

With continued reference to FIG. 2, a separator 126, in spaced relationto the transducer discs 120, is retained between a bottom retainingplate 128 and a top retaining plate 130. Gas delivery tubes 132 areconnected to gas distribution manifolds 134, which have gas deliveryports 136. The gas distribution manifolds 134 are housed within agenerator body 138 that is covered by generator lid 140. A transducerdriver 144, having circuitry for driving the transducer discs 120, iselectronically connected with the transducer discs 120 via electricalcables 146.

During operation of the aerosol generator 106, as shown in FIG. 2, thetransducer discs 120 are activated by the transducer driver 144 via theelectrical cables 146. The transducers preferably vibrate at a frequencyof from about 1 MHz to about 5 MHz, more preferably from about 1.5 MHzto about 3 MHz. Commonly used frequencies are at about 1.6 MHz and about2.4 MHz. Furthermore, all of the transducer discs 110 should beoperating at substantially the same frequency when an aerosol with anarrow droplet size distribution is desired. This is important becausecommercially available transducers can vary significantly in thickness,sometimes by as much as 10%. It is preferred, however, that thetransducer discs 120 operate at frequencies within a range of 5% aboveand below the median transducer frequency, more preferably within arange of 2.5%, and most preferably within a range of 1%. This can beaccomplished by careful selection of the transducer discs 120 so thatthey all preferably have thicknesses within 5% of the median transducerthickness, more preferably within 2.5%, and most preferably within 1%.

Liquid feed 102 enters through a feed inlet 148 and flows through flowchannels 150 to exit through feed outlet 152. An ultrasonicallytransmissive fluid, typically water, enters through a water inlet 154 tofill a water bath volume 156 and flow through flow channels 158 to exitthrough a water outlet 160. A proper flow rate of the ultrasonicallytransmissive fluid is necessary to cool the transducer discs 120 and toprevent overheating of the ultrasonically transmissive fluid. Ultrasonicsignals from the transducer discs 120 are transmitted, via theultrasonically transmissive fluid, across the water bath volume 156, andultimately across the separator 126, to the liquid feed 102 in flowchannels 150.

The ultrasonic signals from the ultrasonic transducer discs 120 causeatomization cones 162 to develop in the liquid feed 102 at locationscorresponding with the transducer discs 120. Carrier gas 104 isintroduced into the gas delivery tubes 132 and delivered to the vicinityof the atomization cones 162 via gas delivery ports 136. Jets of carriergas exit the gas delivery ports 136 in a direction so as to impinge onthe atomization cones 162, thereby sweeping away atomized droplets ofthe liquid feed 102 that are being generated from the atomization cones162 and creating the aerosol 108, which exits the aerosol generator 106through an aerosol exit opening 164.

Efficient use of the carrier gas 104 is an important aspect of theaerosol generator 106. The embodiment of the aerosol generator 106 shownin FIG. 2 includes two gas exit ports per atomization cone 162, with thegas ports being positioned above the liquid medium 102 over troughs thatdevelop between the atomization cones 162, such that the exiting carriergas 104 is horizontally directed at the surface of the atomization cones162, thereby efficiently distributing the carrier gas 104 to criticalportions of the liquid feed 102 for effective and efficient sweepingaway of droplets as they form about the ultrasonically energizedatomization cones 162. Furthermore, it is preferred that at least aportion of the opening of each of the gas delivery ports 136, throughwhich the carrier gas exits the gas delivery tubes, should be locatedbelow the top of the atomization cones 162 at which the carrier gas 104is directed. This relative placement of the gas delivery ports 136 isvery important to efficient use of carrier gas 104. Orientation of thegas delivery ports 136 is also important. Preferably, the gas deliveryports 136 are positioned to horizontally direct jets of the carrier gas104 at the atomization cones 162. The aerosol generator 106 permitsgeneration of the aerosol 108 with heavy loading with droplets of thecarrier liquid 102, unlike aerosol generator designs that do notefficiently focus gas delivery to the locations of droplet formation.

Another important feature of the aerosol generator 106, as shown in FIG.2, is the use of the separator 126, which protects the transducer discs120 from direct contact with the liquid feed 102, which is often highlycorrosive. The height of the separator 126 above the top of thetransducer discs 120 should normally be kept as small as possible, andis often in the range of from about 1 centimeter to about 2 centimeters.The top of the liquid feed 102 in the flow channels above the tops ofthe ultrasonic transducer discs 120 is typically in a range of fromabout 2 centimeters to about 5 centimeters, whether or not the aerosolgenerator includes the separator 126, with a distance of about 3 to 4centimeters being preferred. Although the aerosol generator 106 could bemade without the separator 126, in which case the liquid feed 102 wouldbe in direct contact with the transducer discs 120, the highly corrosivenature of the liquid feed 102 can often cause premature failure of thetransducer discs 120. The use of the separator 126, in combination withuse of the ultrasonically transmissive fluid in the water bath volume156 to provide ultrasonic coupling, significantly extending the life ofthe ultrasonic transducers 120. One disadvantage of using the separator126, however, is that the rate of droplet production from theatomization cones 162 is reduced, often by a factor of two or more,relative to designs in which the liquid feed 102 is in direct contactwith the ultrasonic transducer discs 102. Even with the separator 126,however, the aerosol generator 106 used with the present invention iscapable of producing a high quality aerosol with heavy droplet loading,as previously discussed. Suitable materials for the separator 126include, for example, polyamides (such as Kapton® membranes from DuPont)and other polymer materials, glass, and plexiglass. The mainrequirements for the separator 126 are that it be ultrasonicallytransmissive, corrosion resistant and impermeable.

One alternative to using the separator 126 is to bind acorrosion-resistant protective coating onto the surface of theultrasonic transducer discs 120, thereby preventing the liquid feed 102from contacting the surface of the ultrasonic transducer discs 120. Whenthe ultrasonic transducer discs 120 have a protective coating, theaerosol generator 106 will typically be constructed without the waterbath volume 156 and the liquid feed 102 will flow directly over theultrasonic transducer discs 120. Examples of such protective coatingmaterials include platinum, gold, TEFLON®, epoxies and various plastics.Such coating typically significantly extends transducer life. Also, whenoperating without the separator 126, the aerosol generator 106 willtypically produce the aerosol 108 with a much higher droplet loadingthan when the separator 126 is used.

One surprising finding with operation of the aerosol generator 106 ofthe present invention is that the droplet loading in the aerosol may beaffected by the temperature of the liquid feed 102 as well as thetemperature of the water bath volume 156. It has been found that whenthe liquid feed 102 and/or the water bath volume includes an aqueousliquid at an elevated temperature, the droplet loading increasessignificantly. The temperature of the liquid feed 102 and/or the waterbath volume 156 is preferably higher than about 30° C., and morepreferably higher than about 35° C. If the temperature becomes too high,however, it can have a detrimental effect on droplet loading in theaerosol 108. Therefore, the temperature of the liquid feed 102 and/orthe water bath volume should generally be lower than about 50° C., andpreferably lower than about 45° C. Either the liquid feed 102 or thewater bath volume 156 may be maintained at the desired temperature inany suitable fashion. For example, the portion of the aerosol generator106 where the liquid feed 102 is converted to the aerosol 108 could bemaintained at a constant elevated temperature. Alternatively, the liquidfeed 102 could be delivered to the aerosol generator 106 from a constanttemperature bath maintained separate from the aerosol generator 106.

The design for the aerosol generator 106 based on an array of ultrasonictransducers is versatile and is easily modified to accommodate differentgenerator sizes for different specialty applications. The aerosolgenerator 106 may be designed to include a plurality of ultrasonictransducers in any convenient number. Even for smaller scale production,however, the aerosol generator 106 preferably has at least nineultrasonic transducers, more preferably at least 16 ultrasonictransducers, and even more preferably at least 25 ultrasonictransducers. For larger scale production, however, the aerosol generator106 includes at least 40 ultrasonic transducers, more preferably atleast 100 ultrasonic transducers, and even more preferably at least 400ultrasonic transducers. In some large volume applications, the aerosolgenerator may have at least 1000 ultrasonic transducers.

FIGS. 4-21 show component designs for an aerosol generator 106 includingan array of 400 ultrasonic transducers. Referring first to FIGS. 4 and5, the transducer mounting plate 124 is shown with a design toaccommodate an array of 400 ultrasonic transducers, arranged in foursubarrays of 100 ultrasonic transducers each. The transducer mountingplate 124 has integral vertical walls 172 for containing theultrasonically transmissive fluid, typically water, in a water bathsimilar to the water bath volume 156 described previously with referenceto FIG. 2.

As shown in FIGS. 4 and 5, four hundred transducer mounting receptacles174 are provided in the transducer mounting plate 124 for mountingultrasonic transducers for the desired array. With reference to FIG. 6,the profile of an individual transducer mounting receptacle 174 isshown. A mounting seat 176 accepts an ultrasonic transducer formounting, with a mounted ultrasonic transducer being held in place viascrew holes 178. Opposite the mounting receptacle 176 is a flaredopening 180 through which an ultrasonic signal may be transmitted forthe purpose of generating the aerosol 108, as previously described withreference to FIG. 2.

A preferred transducer mounting configuration, however, is shown in FIG.7 for another configuration for the transducer mounting plate 124. Asseen in FIG. 7, an ultrasonic transducer disc 120 is mounted to thetransducer mounting plate 124 by use of a compression screw 177 threadedinto a threaded receptacle 179. The compression screw 177 bears againstthe ultrasonic transducer disc 120, causing an o-ring 181, situated inan o-ring seat 182 on the transducer mounting plate, to be compressed toform a seal between the transducer mounting plate 124 and the ultrasonictransducer disc 120. This type of transducer mounting is particularlypreferred when the ultrasonic transducer disc 120 includes a protectivesurface coating, as discussed previously, because the seal of the o-ringto the ultrasonic transducer disc 120 will be inside of the outer edgeof the protective seal, thereby preventing liquid from penetrating underthe protective surface coating from the edges of the ultrasonictransducer disc 120.

Referring now to FIG. 8, the bottom retaining plate 128 for a 400transducer array is shown having a design for mating with the transducermounting plate 124 (shown in FIGS. 4-5). The bottom retaining plate 128has eighty openings 184, arranged in four subgroups 186 of twentyopenings 184 each. Each of the openings 184 corresponds with five of thetransducer mounting receptacles 174 (shown in FIGS. 4 and 5) when thebottom retaining plate 128 is mated with the transducer mounting plate124 to create a volume for a water bath between the transducer mountingplate 124 and the bottom retaining plate 128. The openings 184,therefore, provide a pathway for ultrasonic signals generated byultrasonic transducers to be transmitted through the bottom retainingplate.

Referring now to FIGS. 9 and 10, a liquid feed box 190 for a 400transducer array is shown having the top retaining plate 130 designed tofit over the bottom retaining plate 128 (shown in FIG. 8), with aseparator 126 (not shown) being retained between the bottom retainingplate 128 and the top retaining plate 130 when the aerosol generator 106is assembled. The liquid feed box 190 also includes vertically extendingwalls 192 for containing the liquid feed 102 when the aerosol generatoris in operation. Also shown in FIGS. 9 and 10 is the feed inlet 148 andthe feed outlet 152. An adjustable weir 198 determines the level ofliquid feed 102 in the liquid feed box 190 during operation of theaerosol generator 106.

The top retaining plate 130 of the liquid feed box 190 has eightyopenings 194 therethrough, which are arranged in four subgroups 196 oftwenty openings 194 each. The openings 194 of the top retaining plate130 correspond in size with the openings 184 of the bottom retainingplate 128 (shown in FIG. 8). When the aerosol generator 106 isassembled, the openings 194 through the top retaining plate 130 and theopenings 184 through the bottom retaining plate 128 are aligned, withthe separator 126 positioned therebetween, to permit transmission ofultrasonic signals when the aerosol generator 106 is in operation.

Referring now to FIGS. 9-11, a plurality of gas tube feed-through holes202 extend through the vertically extending walls 192 to either side ofthe assembly including the feed inlet 148 and feed outlet 152 of theliquid feed box 190. The gas tube feed-through holes 202 are designed topermit insertion therethrough of gas tubes 208 of a design as shown inFIG. 11. When the aerosol generator 106 is assembled, a gas tube 208 isinserted through each of the gas tube feed-through holes 202 so that gasdelivery ports 136 in the gas tube 208 will be properly positioned andaligned adjacent the openings 194 in the top retaining plate 130 fordelivery of gas to atomization cones that develop in the liquid feed box190 during operation of the aerosol generator 106. The gas deliveryports 136 are typically holes having a diameter of from about 1.5millimeters to about 3.5 millimeters.

Referring now to FIG. 12, a partial view of the liquid feed box 190 isshown with gas tubes 208A, 208B and 208C positioned adjacent to theopenings 194 through the top retaining plate 130. Also shown in FIG. 12are the relative locations that ultrasonic transducer discs 120 wouldoccupy when the aerosol generator 106 is assembled. As seen in FIG. 12,the gas tube 208A, which is at the edge of the array, has five gasdelivery ports 136. Each of the gas delivery ports 136 is positioned todivert carrier gas 104 to a different one of atomization cones thatdevelop over the array of ultrasonic transducer discs 120 when theaerosol generator 106 is operating. The gas tube 208B, which is one rowin from the edge of the array, is a shorter tube that has ten gasdelivery ports 136, five each on opposing sides of the gas tube 208B.The gas tube 208B, therefore, has gas delivery ports 136 for deliveringgas to atomization cones corresponding with each of ten ultrasonictransducer discs 120. The third gas tube, 208C, is a longer tube thatalso has ten gas delivery ports 136 for delivering gas to atomizationcones corresponding with ten ultrasonic transducer discs 120. The designshown in FIG. 12, therefore, includes one gas delivery port perultrasonic transducer disc 120. Although this is a lower density of gasdelivery ports 136 than for the embodiment of the aerosol generator 106shown in FIG. 2, which includes two gas delivery ports per ultrasonictransducer disc 120, the design shown in FIG. 12 is, nevertheless,capable of producing a dense, high-quality aerosol without unnecessarywaste of gas.

Referring now to FIG. 13, the flow of carrier gas 104 relative toatomization cones 162 during operation of the aerosol generator 106having a gas distribution configuration to deliver carrier gas 104 fromgas delivery ports on both sides of the gas tubes 208, as was shown forthe gas tubes 208A, 208B and 208C in the gas distribution configurationshown in FIG. 11. The carrier gas 104 sweeps both directions from eachof the gas tubes 208.

An alternative, and preferred, flow for carrier gas 104 is shown in FIG.14. As shown in FIG. 14, carrier gas 104 is delivered from only one sideof each of the gas tubes 208. This results in a sweep of carrier gasfrom all of the gas tubes 208 toward a central area 212. This results ina more uniform flow pattern for aerosol generation that maysignificantly enhance the efficiency with which the carrier gas 104 isused to produce an aerosol. The aerosol that is generated, therefore,tends to be more heavily loaded with liquid droplets.

Another configuration for distributing carrier gas in the aerosolgenerator 106 is shown in FIGS. 15 and 16. In this configuration, thegas tubes 208 are hung from a gas distribution plate 216 adjacent gasflow holes 218 through the gas distribution plate 216. In the aerosolgenerator 106, the gas distribution plate 216 would be mounted above theliquid feed, with the gas flow holes positioned to each correspond withan underlying ultrasonic transducer. Referring specifically to FIG. 16,when the ultrasonic generator 106 is in operation, atomization cones 162develop through the gas flow holes 218, and the gas tubes 208 arelocated such that carrier gas 104 exiting from ports in the gas tubes208 impinge on the atomization cones and flow upward through the gasflow holes. The gas flow holes 218, therefore, act to assist inefficiently distributing the carrier gas 104 about the atomization cones162 for aerosol formation. It should be appreciated that the gasdistribution plates 218 can be made to accommodate any number of the gastubes 208 and gas flow holes 218. For convenience of illustration, theembodiment shown in FIGS. 15 and 16 shows a design having only two ofthe gas tubes 208 and only 16 of the gas flow holes 218. Also, it shouldbe appreciated that the gas distribution plate 216 could be used alone,without the gas tubes 208. In that case, a slight positive pressure ofcarrier gas 104 would be maintained under the gas distribution plate 216and the gas flow holes 218 would be sized to maintain the propervelocity of carrier gas 104 through the gas flow holes 218 for efficientaerosol generation. Because of the relative complexity of operating inthat mode, however, it is not preferred.

Aerosol generation may also be enhanced through mounting of ultrasonictransducers at a slight angle and directing the carrier gas at resultingatomization cones such that the atomization cones are tilting in thesame direction as the direction of flow of carrier gas. Referring toFIG. 17, an ultrasonic transducer disc 120 is shown. The ultrasonictransducer disc 120 is tilted at a tilt angle 114 (typically less than10 degrees), so that the atomization cone 162 will also have a tilt. Itis preferred that the direction of flow of the carrier gas 104 directedat the atomization cone 162 is in the same direction as the tilt of theatomization cone 162.

Referring now to FIGS. 18 and 19, a gas manifold 220 is shown fordistributing gas to the gas tubes 208 in a 400 transducer array design.The gas manifold 220 includes a gas distribution box 222 and pipingstubs 224 for connection with gas tubes 208 (shown in FIG. 11). Insidethe gas distribution box 222 are two gas distribution plates 226 thatform a flow path to assist in distributing the gas equally throughoutthe gas distribution box 222, to promote substantially equal delivery ofgas through the piping stubs 224. The gas manifold 220, as shown inFIGS. 18 and 19, is designed to feed eleven gas tubes 208. For the 400transducer design, a total of four gas manifolds 220 are required.

Referring now to FIGS. 23 and 24, the generator lid 140 is shown for a400 transducer array design. The generator lid 140 mates with and coversthe liquid feed box 190 (shown in FIGS. 9 and 10). The generator lid140, as shown in FIGS. 20 and 21, has a hood design to permit easycollection of the aerosol 108 without subjecting droplets in the aerosol108 to sharp edges on which droplets may coalesce and be lost, andpossibly interfere with the proper operation of the aerosol generator106. When the aerosol generator 106 is in operation, the aerosol 108would be withdrawn via the aerosol exit opening 164 through thegenerator cover 140.

It is important that the aerosol stream that is fed to the furnace 110have a high droplet flow rate and high droplet loading as would berequired for most industrial applications. With the present invention,the aerosol stream fed to the furnace preferably includes a droplet flowof greater than about 0.5 liters per hour, more preferably greater thanabout 2 liters per hour, still more preferably greater than about 5liters per hour, even more preferably greater than about 10 liters perhour, particularly greater than about 50 liters per hour and mostpreferably greater than about 100 liters per hour; and with the dropletloading being typically greater than about 0.04 milliliters of dropletsper liter of carrier gas, preferably greater than about 0.083milliliters of droplets per liter of carrier gas 104, more preferablygreater than about 0.167 milliliters of droplets per liter of carriergas 104, still more preferably greater than about 0.25 milliliters ofdroplets per liter of carrier gas 104, particularly greater than about0.33 milliliters of droplets per liter of carrier gas 104 and mostpreferably greater than about 0.83 milliliters of droplets per liter ofcarrier gas 104.

In addition to the foregoing, it has been found to be advantageousaccording to the present invention to provide means for adjusting theconcentration of precursor in the liquid feed. More specifically, it hasbeen found that during aerosol production, the precursor solution canconcentrate due to the preferential evaporation of water from theliquid. As a result, it is desirable to provide water to the liquideither on a substantially continuous basis or periodically to maintainthe concentration of the precursors within an acceptable range. In someinstances, it may also be necessary to add small amounts of precursorsif there is any preferential evaporation of precursor materials from theliquid.

The aerosol generator 106 of the present invention produces aconcentrated, high quality aerosol of micro-sized droplets having arelatively narrow size distribution. It has been found, however, thatfor many applications the process of the present invention issignificantly enhanced by further classifying by size the droplets inthe aerosol 108 prior to introduction of the droplets into the furnace110. In this manner, the size and size distribution of particles in theparticulate product 116 are further controlled.

Referring now to FIG. 22, a process flow diagram is shown for oneembodiment of the process of the present invention including suchdroplet classification. As shown in FIG. 22, the aerosol 108 from theaerosol generator 106 goes to a droplet classifier 280 where oversizeddroplets are removed from the aerosol 108 to prepare a classifiedaerosol 282. Liquid 284 from the oversized droplets that are beingremoved is drained from the droplet classifier 280. This drained liquid284 may advantageously be recycled for use in preparing additionalliquid feed 102.

Any suitable droplet classifier may be used for removing droplets abovea predetermined size. For example, a cyclone could be used to removeover-size droplets. A preferred droplet classifier for manyapplications, however, is an impactor. One embodiment of an impactor foruse with the present invention will now be described with reference toFIGS. 23-27.

As seen in FIG. 23, an impactor 288 has disposed in a flow conduit 286 aflow control plate 290 and an impactor plate assembly 292. The flowcontrol plate 290 is conveniently mounted on a mounting plate 294.

The flow control plate 290 is used to channel the flow of the aerosolstream toward the impactor plate assembly 292 in a manner withcontrolled flow characteristics that are desirable for proper impactionof oversize droplets on the impactor plate assembly 292 for removalthrough the drains 296 and 314. One embodiment of the flow control plate290 is shown in FIG. 24. The flow control plate 290 has an array ofcircular flow ports 296 for channeling flow of the aerosol 108 towardsthe impactor plate assembly 292 with the desired flow characteristics.

Details of the mounting plate 294 are shown in FIG. 25. The mountingplate 294 has a mounting flange 298 with a large diameter flow opening300 passing therethrough to permit access of the aerosol 108 to the flowports 296 of the flow control plate 290 (shown in FIG. 24).

Referring now to FIGS. 26 and 27, one embodiment of an impactor plateassembly 292 is shown. The impactor plate assembly 292 includes animpactor plate 302 and mounting brackets 304 and 306 used to mount theimpactor plate 302 inside of the flow conduit 286. The impactor plate302 and the flow channel plate 290 are designed so that droplets largerthan a predetermined size will have momentum that is too large for thoseparticles to change flow direction to navigate around the impactor plate302.

During operation of the impactor 288, the aerosol 108 from the aerosolgenerator 106 passes through the upstream flow control plate 290. Mostof the droplets in the aerosol navigate around the impactor plate 302and exit the impactor 288 through the downstream flow control plate 290in the classified aerosol 282. Droplets in the aerosol 108 that are toolarge to navigate around the impactor plate 302 will impact on theimpactor plate 302 and drain through the drain 296 to be collected withthe drained liquid 284 (as shown in FIG. 23).

The configuration of the impactor plate 302 shown in FIG. 22 representsonly one of many possible configurations for the impactor plate 302. Forexample, the impactor 288 could include an upstream flow control plate290 having vertically extending flow slits therethrough that are offsetfrom vertically extending flow slits through the impactor plate 302,such that droplets too large to navigate the change in flow due to theoffset of the flow slits between the flow control plate 290 and theimpactor plate 302 would impact on the impactor plate 302 to be drainedaway. Other designs are also possible.

In a preferred embodiment of the present invention, the dropletclassifier 280 is typically designed to remove droplets from the aerosol108 that are larger than about 15 μm in size, more preferably to removedroplets larger than about 10 μm in size, even more preferably to removedroplets of a size larger than about 8 μm in size and most preferably toremove droplets larger than about 5 μm in size. The dropletclassification size in the droplet classifier is preferably smaller thanabout 15 μm, more preferably smaller than about 10 μm, even morepreferably smaller than about 8 μm and most preferably smaller thanabout 5 μm. The classification size, also called the classification cutpoint, is that size at which half of the droplets of that size areremoved and half of the droplets of that size are retained. Dependingupon the specific application, however, the droplet classification sizemay be varied, such as by changing the spacing between the impactorplate 302 and the flow control plate 290 or increasing or decreasingaerosol velocity through the jets in the flow control plate 290. Becausethe aerosol generator 106 of the present invention initially produces ahigh quality aerosol 108, having a relatively narrow size distributionof droplets, typically less than about 30 weight percent of liquid feed102 in the aerosol 108 is removed as the drain liquid 284 in the dropletclassifier 288, with preferably less than about 25 weight percent beingremoved, even more preferably less than about 20 weight percent beingremoved and most preferably less than about 15 weight percent beingremoved. Minimizing the removal of liquid feed 102 from the aerosol 108is particularly important for commercial applications to increase theyield of high quality particulate product 116. It should be noted,however, that because of the superior performance of the aerosolgenerator 106, it is frequently not required to use an impactor or otherdroplet classifier to obtain a desired absence of oversize droplets tothe furnace. This is a major advantage, because the added complexity andliquid losses accompanying use of an impactor may often be avoided withthe process of the present invention.

With some applications of the process of the present invention, it maybe possible to collect the particles 112 directly from the output of thefurnace 110. More often, however, it will be desirable to cool theparticles 112 exiting the furnace 110 prior to collection of theparticles 112 in the particle collector 114. Referring now to FIG. 28,one embodiment of the process of the present invention is shown in whichthe particles 112 exiting the furnace 110 are sent to a particle cooler320 to produce a cooled particle stream 322, which is then feed to theparticle collector 114. Although the particle cooler 320 may be anycooling apparatus capable of cooling the particles 112 to the desiredtemperature for introduction into the particle collector 114,traditional heat exchanger designs are not preferred. This is because atraditional heat exchanger design ordinarily directly subjects theaerosol stream, in which the hot particles 112 are suspended, to coolsurfaces. In that situation, significant losses of the particles 112occur due to thermophoretic deposition of the hot particles 112 on thecool surfaces of the heat exchanger. According to the present invention,a gas quench apparatus is provided for use as the particle cooler 320that significantly reduces thermophoretic losses compared to atraditional heat exchanger.

Referring now to FIGS. 29-31, one embodiment of a gas quench cooler 330is shown. The gas quench cooler includes a perforated conduit 332 housedinside of a cooler housing 334 with an annular space 336 located betweenthe cooler housing 334 and the perforated conduit 332. In fluidcommunication with the annularspace 336 is a quench gas inlet box 338,inside of which is disposed a portion of an aerosol outlet conduit 340.The perforated conduit 332 extends between the aerosol outlet conduit340 and an aerosol inlet conduit 342. Attached to an opening into thequench gas inlet box 338 are two quench gas feed tubes 344. Referringspecifically to FIG. 31, the perforated tube 332 is shown. Theperforated tube 332 has a plurality of openings 345. The openings 345,when the perforated conduit 332 is assembled into the gas quench cooler330, permit the flow of quench gas 346 from the annular space 336 intothe interior space 348 of the perforated conduit 332. Although theopenings 345 are shown as being round holes, any shape of opening couldbe used, such as slits. Also, the perforated conduit 332 could be aporous screen. Two heat radiation shields 347 prevent downstream radiantheating from the furnace. In most instances, however, it will not benecessary to include the heat radiation shields 347, because downstreamradiant heating from the furnace is normally not a significant problem.Use of the heat radiation shields 347 is not preferred due toparticulate losses that accompany their use.

With continued reference to FIGS. 29-31, operation of the gas quenchcooler 330 will now be described. During operation, the particles 112,carried by and dispersed in a gas stream, enter the gas quench cooler330 through the aerosol inlet conduit 342 and flow into the interiorspace 348 of perforated conduit 332. Quench gas 346 is introducedthrough the quench gas feed tubes 344 into the quench gas inlet box 338.Quench gas 346 entering the quench gas inlet box 338 encounters theouter surface of the aerosol outlet conduit 340, forcing the quench gas346 to flow, in a spiraling, swirling manner, into the annular space336, where the quench gas 346 flows through the openings 345 through thewalls of the perforated conduit 332. Preferably, the gas 346 retainssome swirling motion even after passing into the interior space 348. Inthis way, the particles 112 are quickly cooled with low losses ofparticles to the walls of the gas quench cooler 330. In this manner, thequench gas 346 enters in a radial direction into the interior space 348of the perforated conduit 332 around the entire periphery, orcircumference, of the perforated conduit 332 and over the entire lengthof the perforated conduit 332. The cool quench gas 346 mixes with andcools the hot particles 112, which then exit through the aerosol outletconduit 340 as the cooled particle stream 322. The cooled particlestream 322 can then be sent to the particle collector 114 for particlecollection. The temperature of the cooled particle stream 322 iscontrolled by introducing more or less quench gas. Also, as shown inFIG. 29, the quench gas 346 is fed into the quench cooler 330 in counterflow to flow of the particles. Alternatively, the quench cooler could bedesigned so that the quench gas 346 is fed into the quench cooler inconcurrent flow with the flow of the particles 112. The amount of quenchgas 346 fed to the gas quench cooler 330 will depend upon the specificmaterial being made and the specific operating conditions. The quantityof quench gas 346 used, however, must be sufficient to reduce thetemperature of the aerosol steam including the particles 112 to thedesired temperature. Typically, the particles 112 are cooled to atemperature at least below about 200° C., and often lower. The onlylimitation on how much the particles 112 are cooled is that the cooledparticle stream 322 must be at a temperature that is above thecondensation temperature for water as another condensible vapor in thestream. The temperature of the cooled particle stream 322 is often at atemperature of from about 50° C. to about 120° C.

Because of the entry of quench gas 346 into the interior space 348 ofthe perforated conduit 322 in a radial direction about the entirecircumference and length of the perforated conduit 322, a buffer of thecool quench gas 346 is formed about the inner wall of the perforatedconduit 332, thereby significantly inhibiting the loss of hot particles112 due to thermophoretic deposition on the cool wall of the perforatedconduit 332. In operation, the quench gas 346 exiting the openings 345and entering into the interior space 348 should have a radial velocity(velocity inward toward the center of the circular cross-section of theperforated conduit 332) of larger than the thermophoretic velocity ofthe particles 112 inside the perforated conduit 332 in a directionradially outward toward the perforated wall of the perforated conduit332.

As seen in FIGS. 29-31, the gas quench cooler 330 includes a flow pathfor the particles 112 through the gas quench cooler of a substantiallyconstant cross-sectional shape and area. Preferably, the flow paththrough the gas quench cooler 330 will have the same cross-sectionalshape and area as the flow path through the furnace 110 and through theconduit delivering the aerosol 108 from the aerosol generator 106 to thefurnace 110. In one embodiment, however, it may be necessary to reducethe cross-sectional area available for flow prior to the particlecollector 114. This is the case, for example, when the particlecollector includes a cyclone for separating particles in the cooledparticle stream 322 from gas in the cooled particle stream 322. This isbecause of the high inlet velocity requirements into cyclone separators.

Referring now to FIG. 32, one embodiment of the gas quench cooler 330 isshown in combination with a cyclone separator 392. The perforatedconduit 332 has a continuously decreasing cross-sectional area for flowto increase the velocity of flow to the proper value for the feed tocyclone separator 392. Attached to the cyclone separator 392 is a bagfilter 394 for final clean-up of overflow from the cyclone separator392. Separated particles exit with underflow from the cyclone separator392 and may be collected in any convenient container. The use of cycloneseparation is particularly preferred for powder having a weight averagesize of larger than about 1 μm, although a series of cyclones maysometimes be needed to get the desired degree of separation. Cycloneseparation is particularly preferred for powders having a weight averagesize of larger than about 1.5 μm. Also, cyclone separation is bestsuited for high density materials. Preferably, when particles areseparated using a cyclone, the particles are of a composition withspecific gravity of greater than about 5.

In an additional embodiment, the process of the present invention canalso incorporate compositional modification of the particles 112 exitingthe furnace. Most commonly, the compositional modification will involveforming on the particles 112 a material phase that is different thanthat of the particles 112, such as by coating the particles 112 with acoating material. One embodiment of the process of the present inventionincorporating particle coating is shown in FIG. 33. As shown in FIG. 33,the particles 112 exiting from the furnace 110 go to a particle coater350 where a coating is placed over the outer surface of the particles112 to form coated particles 352, which are then sent to the particlecollector 114 for preparation of the particulate product 116. Coatingmethodologies employed in the particle coater 350 are discussed in moredetail below.

With continued reference primarily to FIG. 33, in a preferredembodiment, when the particles 112 are coated according to the processof the present invention, the particles 112 are also manufactured viathe aerosol process of the present invention, as previously described.The process of the present invention can, however, be used to coatparticles that have been premanufactured by a different process, such asby a liquid precipitation route. When coating particles that have beenpremanufactured by a different route, such as by liquid precipitation,it is preferred that the particles remain in a dispersed state from thetime of manufacture to the time that the particles are introduced inslurry form into the aerosol generator 106 for preparation of theaerosol 108 to form the dry particles 112 in the furnace 110, whichparticles 112 can then be coated in the particle coater 350. Maintainingparticles in a dispersed state from manufacture through coating avoidsproblems associated with agglomeration and redispersion of particles ifparticles must be redispersed in the liquid feed 102 for feed to theaerosol generator 106. For example, for particles originallyprecipitated from a liquid medium, the liquid medium containing thesuspended precipitated particles could be used to form the liquid feed102 to the aerosol generator 106. It should be noted that the particlecoater 350 could be an integral extension of the furnace 110 or could bea separate piece of equipment.

In a further embodiment of the present invention, following preparationof the particles 112 in the furnace 110, the particles 112 may then bestructurally modified to impart desired physical and chemicalproperties. Referring now to FIG. 34, one embodiment of the process ofthe present invention is shown including such structural particlemodification. The particles 112 exiting the furnace 110 go to a particlemodifier 360 where the particles are structurally modified to formmodified particles 362, which are then sent to the particle collector114 for preparation of the particulate product 116. The particlemodifier 360 is typically a furnace, such as an annealing furnace, whichmay be integral with the furnace 110 or may be a separate heatingdevice. Regardless, it is important that the particle modifier 360 havetemperature control that is independent of the furnace 110, so that theproper conditions for particle modification may be provided separatefrom conditions required of the furnace 110 to prepare the particles112. The particle modifier 360, therefore, typically provides atemperature controlled environment and necessary residence time toeffect the desired structural and/or chemical modification of theparticles 112.

The structural modification that occurs in the particle modifier 360 maybe any modification to the crystalline structure or morphology of theparticles 112. Preferably, the particles 112 are heat treated in theparticle modifier 360 to further convert and densify the particles 112or to recrystallize the particles 112 into a polycrystalline or singlecrystalline phosphor form. Also, especially in the case of compositeparticles 112, the particles may be annealed for a sufficient time topermit redistribution within the particles 112 of different materialphases. Particularly preferred parameters for such processes arediscussed in more detail below.

The initial morphology of composite particles made in the furnace 110,according to the present invention, could take a variety of forms,depending upon the specified materials involved and the specificprocessing conditions. Examples of some possible composite particlemorphologies, manufacturable according to the present invention areshown in FIG. 35. These morphologies could be of the particles asinitially produced in the furnace 110 or that result from structuralmodification in the particle modifier 360. Furthermore, the compositeparticles could include a mixture of the morphological attributes shownin FIG. 35.

Aerosol generation with the process of the present invention has thusfar been described with respect to the ultrasonic aerosol generator. Useof the ultrasonic generator is preferred for the process of the presentinvention because of the extremely high quality and dense aerosolgenerated. In some instances, however, the aerosol generation for theprocess of the present invention may have a different design dependingupon the specific application. For example, when larger particles aredesired, such as those having a weight average size of larger than about3 μm, a spray nozzle atomizer may be preferred. For smaller-particleapplications, however, and particularly for those applications toproduce particles smaller than about 3 μm, and preferably smaller thanabout 2 μm in size, as is generally desired with the phosphor particlesof the present invention, the ultrasonic generator, as described herein,is particularly preferred. In that regard, the ultrasonic generator ofthe present invention is particularly preferred for when makingparticles with a weight average size of from about 0.2 μm to about 3 μm.

Although ultrasonic aerosol generators have been used for medicalapplications and home humidifiers, use of ultrasonic generators forspray pyrolysis particle manufacture has largely been confined tosmall-scale, experimental situations. The ultrasonic aerosol generatorof the present invention described with reference to FIGS. 5-24,however, is well suited for commercial production of high qualitypowders with a small average size and a narrow size distribution. Inthat regard, the aerosol generator produces a high quality aerosol, withheavy droplet loading and at a high rate of production. Such acombination of small droplet size, narrow size distribution, heavydroplet loading, and high production rate provide significant advantagesover existing aerosol generators that usually suffer from at least oneof inadequately narrow size distribution, undesirably low dropletloading, or unacceptably low production rate.

Through the careful and controlled design of the ultrasonic generator ofthe present invention, an aerosol may be produced typically havinggreater than about 70 weight percent (and preferably greater than about80 weight percent) of droplets in the size range of from about 1 μm toabout 10 μm, preferably in a size range of from about 1 μm to about 5 μmand more preferably from about 2 μm to about 4 μm. Also, the ultrasonicgenerator of the present invention is capable of delivering high outputrates of liquid feed in the aerosol. The rate of liquid feed, at thehigh liquid loadings previously described, is preferably greater thanabout 25 milliliters per hour per transducer, more preferably greaterthan about 37.5 milliliters per hour per transducer, even morepreferably greater than about 50 milliliters per hour per transducer andmost preferably greater than about 100 millimeters per hour pertransducer. This high level of performance is desirable for commercialoperations and is accomplished with the present invention with arelatively simple design including a single precursor bath over an arrayof ultrasonic transducers. The ultrasonic generator is made for highaerosol production rates at a high droplet loading, and with a narrowsize distribution of droplets. The generator preferably produces anaerosol at a rate of greater than about 0.5 liter per hour of droplets,more preferably greater than about 2 liters per hour of droplets, stillmore preferably greater than about 5 liters per hour of droplets, evenmore preferably greater than about 10 liters per hour of droplets andmost preferably greater than about 40 liters per hour of droplets. Forexample, when the aerosol generator has a 400 transducer design, asdescribed with reference to FIGS. 7-24, the aerosol generator is capableof producing a high quality aerosol having high droplet loading aspreviously described, at a total production rate of preferably greaterthan about 10 liters per hour of liquid feed, more preferably greaterthan about 15 liters per hour of liquid feed, even more preferablygreater than about 20 liters per hour of liquid feed and most preferablygreater than about 40 liters per hour of liquid feed.

Under most operating conditions, when using such an aerosol generator,total particulate product produced is preferably greater than about 0.5gram per hour per transducer, more preferably greater than about 0.75gram per hour per transducer, even more preferably greater than about1.0 gram per hour per transducer and most preferably greater than about2.0 grams per hour per transducer. The mass of powder produced per unittime will be influenced by the molecular weight of the compound.

One significant aspect of the process of the present invention formanufacturing particulate materials is the unique flow characteristicsencountered in the furnace relative to laboratory scale systems. Themaximum Reynolds number attained for flow in the furnace 110 with thepresent invention is very high, typically in excess of 500, preferablyin excess of 1,000 and more preferably in excess of 2,000. In mostinstances, however, the maximum Reynolds number for flow in the furnacewill not exceed 10,000, and preferably will not exceed 5,000. This issignificantly different from lab-scale systems where the Reynolds numberfor flow in a reactor is typically lower than 50 and rarely exceeds 100.

The Reynolds number is a dimensionless quantity characterizing flow of afluid which, for flow through a circular cross sectional conduit isdefined as:

${Re} = \frac{\rho\;{vd}}{\mu}$

-   -   where:        -   ρ=fluid density;        -   v=fluid mean velocity;        -   d=conduit inside diameter; and        -   μ=fluid viscosity.

It should be noted that the values for density, velocity and viscositywill vary along the length of the furnace 110. The maximum Reynoldsnumber in the furnace 110 is typically attained when the average streamtemperature is at a maximum, because the gas velocity is at a very highvalue due to gas expansion when heated.

One problem with operating under flow conditions at a high Reynoldsnumber is that undesirable volatilization of components is much morelikely to occur than in systems having flow characteristics as found inlaboratory-scale systems. The volatilization problem occurs with thepresent invention, because the furnace is typically operated over asubstantial section of the heating zone in a constant wall heat fluxmode, due to limitations in heat transfer capability. This issignificantly different than operation of a furnace at a laboratoryscale, which typically involves operation of most of the heating zone ofthe furnace in a uniform wall temperature mode, because the heating loadis sufficiently small that the system is not heat transfer limited.

With the present invention, it is typically preferred to heat theaerosol stream in the heating zone of the furnace as quickly as possibleto the desired temperature range for particle manufacture. Because offlow characteristics in the furnace and heat transfer limitations,during rapid heating of the aerosol the wall temperature of the furnacecan significantly exceed the maximum average target temperature for thestream. This is a problem because, even though the average streamtemperature may be within the range desired, the wall temperature maybecome so hot that components in the vicinity of the wall are subjectedto temperatures high enough to undesirably volatilize the components.This volatilization near the wall of the furnace can cause formation ofsignificant quantities of ultrafine particles that are outside of thesize range desired.

Therefore, with the present invention, it is preferred that when theflow characteristics in the furnace are such that the Reynolds numberthrough any part of the furnace exceeds 500, more preferably exceeds1,000, and most preferably exceeds 2,000, the maximum wall temperaturein the furnace should be kept at a temperature that is below thetemperature at which a desired component of the final particles wouldexert a vapor pressure not exceeding about 200 millitorr, morepreferably not exceeding about 100 millitorr, and most preferably notexceeding about 50 millitorr. Furthermore, the maximum wall temperaturein the furnace should also be kept below a temperature at which anintermediate component, from which a final component is to be at leastpartially derived, should also have a vapor pressure not exceeding themagnitudes noted for components of the final product.

In addition to maintaining the furnace wall temperature below a levelthat could create volatilization problems, it is also important thatthis not be accomplished at the expense of the desired average streamtemperature. The maximum average stream temperature must be maintainedat a high enough level so that the particles will have a desired highdensity. The maximum average stream temperature should, however,generally be a temperature at which a component in the final particles,or an intermediate component from which a component in the finalparticles is at least partially derived, would exert a vapor pressurenot exceeding about 100 millitorr, preferably not exceeding about 50millitorr, and most preferably not exceeding about 25 millitorr.

So long as the maximum wall temperature and the average streamtemperature are kept below the point at which detrimental volatilizationoccurs, it is generally desirable to heat the stream as fast as possibleand to remove resulting particles from the furnace immediately after themaximum stream temperature is reached in the furnace. With the presentinvention, the average residence time in the heating zone of the furnacemay typically be maintained at shorter than about 4 seconds, such asfrom about 1 to 2 seconds.

Another significant issue with respect to operating the process of thepresent invention, which includes high aerosol flow rates, is losswithin the system of materials intended for incorporation into the finalparticulate product. Material losses in the system can be quite high ifthe system is not properly operated. If system losses are too high, theprocess would not be practical for use in the manufacture of particulateproducts of many materials. This has typically not been a majorconsideration with laboratory-scale systems.

One significant potential for loss with the process of the presentinvention is thermophoretic losses that occur when a hot aerosol streamis in the presence of a cooler surface. In that regard, the use of thequench cooler, as previously described, with the process of the presentinvention provides an efficient way to cool the particles withoutunreasonably high thermophoretic losses. There is also, however,significant potential for losses occurring near the end of the furnaceand between the furnace and the cooling unit.

It has been found that thermophoretic losses in the back end of thefurnace can be significantly controlled if the heating zone of thefurnace is operated such that the maximum stream temperature is notattained until near the end of the heating zone in the furnace, and atleast not until the last third of the heating zone. When the heatingzone includes a plurality of heating sections, the maximum averagestream temperature should ordinarily not occur until at least the lastheating section. Furthermore, the heating zone should typically extendto as close to the exit of the furnace as possible. This is counter toconventional thought which is to typically maintain the exit portion ofthe furnace at a low temperature to avoid having to seal the furnaceoutlet at a high temperature. Such cooling of the exit portion of thefurnace, however, significantly promotes thermophoretic losses.Furthermore, the potential for operating problems that could result inthermophoretic losses at the back end of the furnace are reduced withthe very short residence times in the furnace for the present invention,as discussed previously.

Typically, it would be desirable to instantaneously cool the aerosolupon exiting the furnace. This is not possible. It is possible, however,to make the residence time between the furnace outlet and the coolingunit as short as possible. Furthermore, it is desirable to insulate theaerosol conduit occurring between the furnace exit and the cooling unitentrance. Even more preferred is to insulate that conduit and, even morepreferably, to also heat that conduit so that the wall temperature ofthat conduit is at least as high as the average stream temperature ofthe aerosol stream. Furthermore, it is desirable that the cooling unitoperate in a manner such that the aerosol is quickly cooled in a mannerto prevent thermophoretic losses during cooling. The quench cooler,described previously, is very effective for cooling with low losses.Furthermore, to keep the potential for thermophoretic losses very low,it is preferred that the residence time of the aerosol stream betweenattaining the maximum stream temperature in the furnace and a point atwhich the aerosol has been cooled to an average stream temperature belowabout 200° C. is shorter than about 2 seconds, more preferably shorterthan about 1 second, and even more preferably shorter than about 0.5second and most preferably shorter than about 0.1 second. In mostinstances, the maximum average stream temperature attained in thefurnace will be greater than about 700° C. Furthermore, the totalresidence time from the beginning of the heating zone in the furnace toa point at which the average stream temperature is at a temperaturebelow about 200° C. should typically be shorter than about 5 seconds,preferably shorter than about 3 seconds, more preferably shorter thanabout 2 seconds, and most preferably shorter than about 1 second.

Another part of the process with significant potential forthermophoretic losses is after particle cooling until the particles arefinally collected. Proper particle collection is very important toreducing losses within the system. The potential for thermophoreticlosses is significant following particle cooling because the aerosolstream is still at an elevated temperature to prevent detrimentalcondensation of water in the aerosol stream. Therefore, cooler surfacesof particle collection equipment can result in significantthermophoretic losses.

To reduce the potential for thermophoretic losses before the particlesare finally collected, it is important that the transition between thecooling unit and particle collection be as short as possible.Preferably, the output from the quench cooler is immediately sent to aparticle separator, such as a filter unit or a cyclone. In that regard,the total residence time of the aerosol between attaining the maximumaverage stream temperature in the furnace and the final collection ofthe particles is preferably shorter than about 2 seconds, morepreferably shorter than about 1 second, still more preferably shorterthan about 0.5 second and most preferably shorter than about 0.1 second.Furthermore, the residence time between the beginning of the heatingzone in the furnace and final collection of the particles is preferablyshorter than about 6 seconds, more preferably shorter than about 3seconds, even more preferably shorter than about 2 seconds, and mostpreferably shorter than about 1 second. Furthermore, the potential forthermophoretic losses may further be reduced by insulating the conduitsection between the cooling unit and the particle collector and, evenmore preferably, by also insulating around the filter, when a filter isused for particle collection. The potential for losses may be reducedeven further by heating of the conduit section between the cooling unitand the particle collection equipment, so that the internal equipmentsurfaces are at least slightly warmer than the aerosol stream averagestream temperature. Furthermore, when a filter is used for particlecollection, the filter could be heated. For example, insulation could bewrapped around a filter unit, with electric heating inside of theinsulating layer to maintain the walls of the filter unit at a desiredelevated temperature higher than the temperature of filter elements inthe filter unit, thereby reducing thermophoretic particle losses towalls of the filter unit.

Even with careful operation to reduce thermophoretic losses, some losseswill still occur. For example, some particles will inevitably be lost towalls of particle collection equipment, such as the walls of a cycloneor filter housing. One way to reduce these losses, and correspondinglyincrease product yield, is to periodically wash the interior of theparticle collection equipment to remove particles adhering to the sides.In most cases, the wash fluid will be water, unless water would have adetrimental effect on one of the components of the particles. Forexample, the particle collection equipment could include parallelcollection paths. One path could be used for active particle collectionwhile the other is being washed. The wash could include an automatic ormanual flush without disconnecting the equipment. Alternatively, theequipment to be washed could be disconnected to permit access to theinterior of the equipment for a thorough wash. As an alternative tohaving parallel collection paths, the process could simply be shut downoccasionally to permit disconnection of the equipment for washing. Theremoved equipment could be replaced with a clean piece of equipment andthe process could then be resumed while the disconnected equipment isbeing washed.

For example, a cyclone or filter unit could periodically be disconnectedand particles adhering to interior walls could be removed by a waterwash. The particles could then be dried in a low temperature dryer,typically at a temperature of lower than about 50° C.

Another area for potential losses in the system, and for the occurrenceof potential operating problems, is between the outlet of the aerosolgenerator and the inlet of the furnace. Losses here are not due tothermophoresis, but rather to liquid coming out of the aerosol andimpinging and collecting on conduit and equipment surfaces. Althoughthis loss is undesirable from a material yield standpoint, the loss maybe even more detrimental to other aspects of the process. For example,water collecting on surfaces may release large droplets that can lead tolarge particles that detrimentally contaminate the particulate product.Furthermore, if accumulated liquid reaches the furnace, the liquid cancause excessive temperature gradients within the furnace tube, which cancause furnace tube failure, especially for ceramic tubes.

One way to reduce the potential for undesirable liquid buildup in thesystem is to provide adequate drains, as previously described. In thatregard, it is preferred that a drain be placed as close as possible tothe furnace inlet to prevent liquid accumulations from reaching thefurnace. The drain should be placed, however, far enough in advance ofthe furnace inlet such that the stream temperature is lower than about80° C. at the drain location.

Another way to reduce the potential for undesirable liquid buildup isfor the conduit between the aerosol generator outlet and the furnaceinlet to be of a substantially constant cross sectional area andconfiguration. Preferably, the conduit beginning with the aerosolgenerator outlet, passing through the furnace and continuing to at leastthe cooling unit inlet is of a substantially constant cross sectionalarea and geometry.

Another way to reduce the potential for undesirable buildup is to heatat least a portion, and preferably the entire length, of the conduitbetween the aerosol generator and the inlet to the furnace. For example,the conduit could be wrapped with a heating tape to maintain the insidewalls of the conduit at a temperature higher than the temperature of theaerosol. The aerosol would then tend to concentrate toward the center ofthe conduit due to thermophoresis. Fewer aerosol droplets would,therefore, be likely to impinge on conduit walls or other surfacesmaking the transition to the furnace.

Another way to reduce the potential for undesirable liquid buildup is tointroduce a dry gas into the aerosol between the aerosol generator andthe furnace. Referring now to FIG. 36, one embodiment of the process isshown for adding a dry gas 118 to the aerosol 108 before the furnace110. Addition of the dry gas 118 causes vaporization of at least a partof the moisture in the aerosol 108, and preferably substantially all ofthe moisture in the aerosol 108, to form a dried aerosol 119, which isthen introduced into the furnace 110.

The dry gas 118 will most often be dry air, although in some instancesit may be desirable to use dry nitrogen gas or some other dry gas. If asufficient quantity of the dry gas 118 is used, the droplets of theaerosol 108 are substantially completely dried to beneficially formdried precursor particles in aerosol form for introduction into thefurnace 110, where the precursor particles are then pyrolyzed to make adesired particulate product. Also, the use of the dry gas 118 typicallywill reduce the potential for contact between droplets of the aerosoland the conduit wall, especially in the critical area in the vicinity ofthe inlet to the furnace 110. In that regard, a preferred method forintroducing the dry gas 118 into the aerosol 108 is from a radialdirection into the aerosol 108. For example, equipment of substantiallythe same design as the quench cooler, described previously withreference to FIGS. 29-31, could be used, with the aerosol 108 flowingthrough the interior flow path of the apparatus and the dry gas 118being introduced through perforated wall of the perforated conduit. Analternative to using the dry gas 118 to dry the aerosol 108 would be touse a low temperature thermal preheater/dryer prior to the furnace 110to dry the aerosol 108 prior to introduction into the furnace 110. Thisalternative is not, however, preferred.

Still another way to reduce the potential for losses due to liquidaccumulation is to operate the process with equipment configurationssuch that the aerosol stream flows in a vertical direction from theaerosol generator to and through the furnace. For smaller-sizeparticles, those smaller than about 1.5 μm, this vertical flow should,preferably, be vertically upward. For larger-size particles, such asthose larger than about 1.5 μm, the vertical flow is preferablyvertically downward.

Furthermore, with the process of the present invention, the potentialfor system losses is significantly reduced because the total systemretention time from the outlet of the generator until collection of theparticles is typically shorter than about 10 seconds, preferably shorterthan about 7 seconds, more preferably shorter than about 5 seconds andmost preferably shorter than about 3 seconds.

Many phosphors, particularly photoluminescent phosphors that are usefulfor plasma display panels, can be difficult to produce usingconventional methods such that the powders have the desirable physical,chemical and luminescent characteristics. Many phosphor compounds can bedifficult to produce even using a standard spray pyrolysis technique.

These compounds can advantageously be produced according to the presentinvention using a process referred to as spray-conversion.Spray-conversion is a process wherein a spray pyrolysis technique, as isdescribed above, is used to produce an intermediate particulate productthat is capable of being subsequently converted to a particulatephosphor having the desirable properties. The intermediate productadvantageously has many of the desirable morphological propertiesdiscussed hereinbelow, such as a small particle size and a narrowparticle size distribution.

As is discussed above, precursor materials including water-solubleprecursors, such as nitrate salts and insoluble precursors such ascolloidal alumina or silica, are placed into solution, atomized and areconverted at a relatively low temperature, such as less than about 1000°C., to intermediate precursor particles that typically include lowcrystallinity oxide phase(s). The intermediate precursor particles havea small size and, preferably, a narrow particle size distribution, as isdescribed in more detail below. The intermediate precursor particles arethen converted by further treatment, such as by heat treating at anelevated temperature, to form a phosphor compound having highcrystallinity and good luminescence characteristics. The resultingpowder advantageously does not require any further milling to reduceparticle size or reduce hard agglomerates since the intermediateparticles have the desired size and hard agglomeration is avoided duringthe subsequent heat treatment. The resulting end product is a highlycrystalline phosphor powder having the desirable morphological andluminescent properties. The average particle size and morphologicalcharacteristics are determined by the characteristics of theintermediate product.

Thus, the precursors can preferably be spray-converted at a temperatureof at least about 700° C., such as from about 750° C. to 950° C., toform a homogeneous admixture including one or more oxides having lowcrystallinity. The intermediate particles can then be heat treated at atemperature of, for example, 1100° C. to 1600° C., to form thesubstantially phase pure phosphor compounds having high crystallinity.

Particularly preferred phosphors that are produced by spray-conversionaccording to the present invention include doped barium magnesiumaluminate (e.g. BaMgAl₁₀O₁₇:Eu or Mn), zinc silicate (e.g. Zn₂SiO₄:Mn),yttria (e.g. Y₂O₃:Eu or Tb) yttrium gadolinium borate (e.g.(Y,Gd)BO₃:Eu) and barium aluminate (e.g. BaAl_(X)O_(Y):Mn). Preferredoperating conditions for producing each of these phosphor compounds isdetailed in Table I hereinbelow.

For the production of phosphors according to the present invention, theliquid feed includes the chemical components that will form the phosphorparticles. For example, the liquid feed can include a solution of metalsalts such as nitrates, chlorides, sulfates, hydroxides or oxalates ofthe phosphor components. In addition, the liquid feed can includeparticulate precursors such as SiO₂ or Al₂O₃.

A preferred precursor are the nitrates, such as yttrium nitrate,Y(NO₃)₃:6H₂O, for the production of yttria phosphor particles. Nitratesare typically highly soluble in water and the solutions maintain a lowviscosity, even at high concentrations. A typical reaction mechanism forthe formation of yttria would be:2Y(NO₃)₃+H₂O+heat→Y₂O₃+NO_(x)+H₂O

For yttria, it is preferred to use a precursor concentration of fromabout 5 to about 10 weight percent, more preferably from 5 to 7 weightpercent, based on the equivalent weight of the final compound.

For the production of europium doped barium magnesium aluminate (BAM:Eu)phosphors according to the present invention, the liquid feed caninclude a solution of metal salts such as nitrates, chlorides, sulfates,hydroxides or oxalates of the phosphor components. According to apreferred embodiment, BAM:Eu is formed from a precursor solutioncomprising barium nitrate, magnesium nitrate and fumed (particulate)alumina for the BAM host material, as well as europium nitrate toprovide the Eu dopant ion or manganese nitrate to provide the Mn dopantion. It has been found that aluminum nitrate as a precursor to aluminumoxide is not a preferred alternative due to solubility limits of bariumnitrate. Therefore it is preferable to use particulate alumina, or asimilar aluminum compound such as boehmite. It has also been foundunexpectedly that the precursor solution should include an amount ofaluminum that is in excess of the stoichiometric amount required to formBAM. In one preferred embodiment, at least about 20 atomic percentexcess alumina is added to the precursor solution. Barium aluminate canbe formed in a similar manner. About 5 to 10 weight percent of theprecursors is preferred.

Preferred precursors for the production of Zn₂SiO₄:Mn include metalssalts, particularly nitrate salts, for the Zn and the Mn. For the silicacomponent, it is preferred to use dispersed particulate silica. It hasalso been found that for the production of zinc silicate that theprecursor solution should include an excess of silica. It has been foundthat, for example, a preferred precursor solution includes an excess ofabout 10 atomic percent silica. It is preferred to use a precursorconcentration of from about 5 to about 10 weight percent, morepreferably from about 6 to 8 weight percent, based on the equivalentweight of the phosphor compound.

(Y,Gd)BO₃ can be formed from a precursor solution comprising yttrium andgadolinium salts, such as the nitrate salts, as well as boric acid.Preferably the precursor solution includes on excess of boric acid,which advantageously produces highly crystalline (Y,Gd)BO₃ powders. Itis preferred to use a precursor concentration of from about 5 to about10 weight percent, more preferably from about 7 to 8 weight percent,based on the equivalent weight of the phosphor compound.

The solution is preferably not saturated with the precursor to avoidprecipitate formation in the liquid. The solution preferably includes,for example, sufficient precursor to yield from about 1 to 50 weightpercent, such as from about 1 to 15 weight percent, of the phosphorcompound. That is, the solution concentrations discussed above aremeasured based on the equivalent weight percent of the product. Thefinal particle size of the phosphor particles is also influenced by theprecursor concentration. Generally, lower precursor concentrations inthe liquid feed will produce particles having a smaller average size.

As is discussed above, the liquid feed preferably includes the dopant(activator ion) precursor. For example, for the production of Y₂O₃:Euphosphor particles, the precursor solution preferably includes yttriumnitrate, as is discussed above, and also europium nitrate. The relativeconcentrations of the precursors can be adjusted to vary theconcentration of the activator ion in the host material.

Preferably, the solvent is aqueous-based for ease of operation, althoughother solvents, such as toluene, may be desirable. However, the use oforganic solvents can lead to undesirable carbon contamination in thephosphor particles. The pH of the aqueous-based solutions can beadjusted to alter the solubility characteristics of the precursors inthe solution.

In addition to the foregoing, the liquid feed may also include otheradditives that contribute to the formation of the particles. Forexample, a fluxing agent can be added to the solution to increase thecrystallinity and/or density of the particles. The addition of urea tometal salt solutions, such as a metal nitrate, can increase the densityof particles produced from the solution. In one embodiment, up to about1 mole equivalent urea is added to the precursor solution, as measuredagainst the moles of phosphor compound in the metal salt solution. Smallamounts, e.g. less than 1 weight percent, of boric acid added to aprecursor solution can also enhance crystallinity without substantiallyaltering the composition of the powder. Further, if the particles are tobe coated phosphor particles, as is discussed in more detail below, asoluble precursor to both the phosphor compound and the coating can beused in the precursor solution wherein the coating precursor is aninvolatile or volatile species.

For producing the phosphor particles, the carrier gas may comprise anygaseous medium in which droplets produced from the liquid feed may bedispersed in aerosol form. Also, the carrier gas may be inert, in thatthe carrier gas does not participate in formation of the phosphorparticles. Alternatively, the carrier gas may have one or more activecomponent(s) that contribute to formation of the phosphor particles. Inthat regard, the carrier gas may include one or more reactive componentsthat react in the furnace to contribute to formation of the phosphorparticles. In many applications for the spray-conversion of phosphorparticles according to the present invention, air will be a satisfactorycarrier gas for providing oxygen. In other instances, a relatively inertgas such as nitrogen may be required.

When the phosphors of the present invention are coated phosphors,precursors to metal oxide coatings can be selected from volatile metalacetates, chlorides, alkoxides or halides. Such precursors are known toreact at high temperatures to form the corresponding metal oxides andeliminate supporting ligands or ions. For example, SiCl₄ can be used asa precursor to SiO₂ coatings when water vapor is present:SiCl_(4(g))+2H₂O_((g))→SiO_(2(s))+4 HCl_((g))SiCl₄ also is highly volatile and is a liquid at room temperature, whichmakes transport into the reactor more controllable.

Metal alkoxides can be used to produce metal oxide films by hydrolysis.The water molecules react with the alkoxide M-O bond resulting in cleanelimination of the corresponding alcohol with the formation of M-O-Mbonds:Si(OEt)₄+2H₂O→SiO₂+4EtOHMost metal alkoxides have a reasonably high vapor pressure and aretherefore well suited as coating precursors.

Metal acetates are also useful as coating precursors since they readilydecompose upon thermal activation by acetic anhydride elimination:Mg(O₂CCH₃)₂→MgO+CH₃C(O)OC(O)CH₃Metal acetates are advantageous as coating precursors since they arewater stable and are reasonably inexpensive.

Coatings can be generated on the particle surface by a number ofdifferent mechanisms. One or more precursors can vaporize and fuse tothe hot phosphor particle surface and thermally react resulting in theformation of a thin-film coating by chemical vapor deposition (CVD).Preferred coatings deposited by CVD include metal oxides and elementalmetals. Further, the coating can be formed by physical vapor deposition(PVD) wherein a coating material physically deposits on the surface ofthe particles. Preferred coatings deposited by PVD include organicmaterials and elemental metals. Alternatively, the gaseous precursor canreact in the gas phase forming small particles, for example less thanabout 5 nanometers in size, which then diffuse to the larger particlesurface and sinter onto the surface, thus forming a coating. This methodis referred to as gas-to-particle conversion (GPC). Whether such coatingreactions occur by CVD, PVD or GPC is dependent on the reactorconditions such as precursor partial pressure, water partial pressureand the concentration of particles in the gas stream. Another possiblesurface coating method is surface conversion of the surface of theparticle by reaction with a vapor phase reactant to convert the surfaceof the particles to a different material than that originally containedin the particles.

In addition, a volatile coating material such as PbO, MoO₃ or V₂O₅ canbe introduced into the reactor such that the coating deposits on theparticle by condensation. Highly volatile metals, such as silver, canalso be deposited by condensation. Further, the phosphor powders can becoated using other techniques. For example, a soluble precursor to boththe phosphor powder and the coating can be used in the precursorsolution wherein the coating precursor is involatile (e.g. Al(NO₃)₃) orvolatile (e.g. Sn(OAc)₄ where OAc is acetate). In another method, acolloidal precursor and a soluble phosphor precursor can be used to forma particulate colloidal coating on the phosphor.

The phosphor powders produced by the foregoing method may be fullyconverted to the crystalline phosphor compound during the pyrolizationstep. However, it is preferred that the powders are spray-converted toan intermediate form. It is then necessary to heat the spray-convertedpowder to convert the intermediate precursor powder to a luminescentphosphor compound and to increase the crystallinity (average crystallitesize) of the powder. Thus, the powders can be heat-treated for an amountof time and in a preselected environment, as is discussed above.Increased crystallinity can advantageously yield an increased brightnessand efficiency of the phosphor particles. If such heat treating stepsare performed, the heat treating temperature and time should be selectedto minimize the amount of interparticle sintering. Table I illustratesexamples of preferred phosphor powders according to the presentinvention with the preferred conversion and heat treatment conditions.

TABLE I Examples of Spray-Converted Phosphor Compounds Conversion HeatHeat Temperature Carrier Treatment Treatment Host Material(pyrolization) Gas Temperature Gas Y₂O₃ 850-1000° C. Air 1350-1500° C.Air BaMgAl₁₀O₁₇  750-950° C. Air 1200-1700° C. H₂/N₂ Zn₂SiO₄  900-950°C. Air 1100-1300° C. Air (Y, Gd) BO₃  900-950° C. Air 1100-1400° C. AirBarium  750-950° C. Air 1200-1700° C. Air Aluminate

A more preferred pyrolization temperature for Y₂O₃ is 900-950° C. Otherpyrolization and heating treatments are possible. For example, BAMprecursor particles can be heated in air at 1200-1600° C. to convert theprecursor to BAM, and then be heated at 1400-1650° C. in ahydrogen-containing gas to reduce Eu³⁺ to Eu²⁺. The heat treatment timeis preferably not more than about 2 hours and can be as little as about1 minute. To reduce agglomeration, the intermediate particles arepreferably heat treated under sufficient agitation to minimize theagglomeration of the particles. One preferred method for agitatingduring heat treatment is to heat treat the powders in a rotary kiln,wherein the powders are constantly moving through a tubular furnace thatis rotating on its major axis.

Further, the crystallinity of the phosphors can be increased by using afluxing agent, either in the precursor solution or in a post-formationannealing step. A fluxing agent is a reagent which improves thecrystallinity of the material when the reagent and the material areheated together, as compared to heating the material to the sametemperature and for the same amount of time in the absence of thefluxing agent. The fluxing agents typically cause a eutectic to formwhich leads to a liquid phase at the grain boundaries, increasing thediffusion coefficient. The fluxing agent, for example alkali metalhalides such as NaCl or KCl or an organic compound such as urea(CO(NH₂)₂), can be added to the precursor solution where it improves thecrystallinity and/or density of the particles during their subsequentformation. Alternatively, the fluxing agent can be contacted with thephosphor powder batches after they have been collected. Upon heattreatment, the fluxing agent improves the crystallinity of the phosphorpowder, and therefore improves other properties such as the brightnessof the phosphor powder. Also, in the case of composite particles, theparticles may be annealed for a sufficient time to permit redistributionwithin the particles of different material phases.

Phosphors are materials which are capable of emitting radiation in thevisible or ultraviolet spectral range upon excitation, such asexcitation by an external electric field or other external energysource. By dispersing combinations of the phosphor powders of thepresent invention, or with other phosphor powders, in a predeterminedarrangement and controllably exciting the powders, a full-color visualdisplay can be achieved.

Phosphors typically include a matrix compound, referred to as a hostmaterial, and the phosphor further includes one or more dopants,referred to as activator ions, to emit a specific color or to enhancethe luminescence characteristics.

The phosphor host material can be doped with an activator ion, typicallyin an amount of from about 0.02 to about 20 atomic percent. Thepreferred concentration of the activator ion will vary depending on thecomposition and the application of the phosphor, as is discussed in moredetail below. The activator ion should also be in the proper oxidationstate, as indicated in Table II.

One advantage of the present invention is that the activator ion ishomogeneously distributed throughout the host material. Phosphor powdersprepared by solid-state methods do not give uniform concentration of theactivator ion in small particles and solution routes also do not givehomogenous distribution of the activator ion due to different rates ofprecipitation.

TABLE II Examples of Photoluminescent Phosphor Materials Host MaterialActivator Ion Color Y₂O₃ Eu³⁺ Red BaMgAl₁₀O₁₇ Eu²⁺ Blue Zn₂SiO₄ Mn²⁺Green (Y, Gd) BO₃ Eu³⁺ Red Barium Mn²⁺ Green Aluminate

The powder characteristics that are preferred will depend upon theapplication of the phosphor powders. Nonetheless, it can be generallystated for most applications that the powders should have a smallparticle size, narrow size distribution, spherical morphology, highdensity/low porosity, high crystallinity and homogenous dopantdistribution of activator ion throughout the host material. Theefficiency of the phosphor, defined as the overall conversion ofexcitation energy to visible photons, should be high.

According to the present invention, the phosphor powder includesparticles having a small average particle size. Although the preferredaverage size of the phosphor particles will vary according to theapplication of the phosphor powder, the average particle size of thephosphor particles is at least about 0.1 μm and not greater than about10 μm. For most applications, the average particle size is preferablynot greater than about 5 μm, such as from about 0.3 μm to about 5 μm andmore preferably is not greater than about 3 μm, such as from about 0.3μm to about 3 μm. As used herein, the average particle size is theweight average particle size.

According to the present invention, the powder batch of phosphorparticles also has a narrow particle size distribution, such that themajority of particles are substantially the same size. Preferably, atleast about 80 weight percent of the particles and more preferably atleast about 90 weight percent of the particles are not larger than twicethe average particle size. Thus, when the average particle size is about2 μm, it is preferred that at least about 80 weight percent of theparticles are not larger than 4 μm and it is more preferred that atleast about 90 weight percent of the particles are not larger than 4 μm.Further, it is preferred that at least about 80 weight percent of theparticles, and more preferably at least about 90 weight percent of theparticles, are not larger than about 1.5 times the average particlesize. Thus, when the average particle size is about 2 μm, it ispreferred that at least about 80 weight percent of the particles are notlarger than about 3 pm and it is more preferred that at least about 90weight percent of the particles are not larger than about 3 μm.

Powders produced by the processes described herein, particularly thosethat have experienced a post treatment step, generally exit as softagglomerates of primary spherical particles. It is well known to thosein the art that micrometer-sized particles often form soft agglomeratesas a result of their relatively high surface energy, as compared tolarger particles. It is also known to those skilled in the art that suchsoft agglomerates may be dispersed easily by treatments such as exposureto ultrasound in a liquid medium or sieving. The average particle sizeand particle size distributions described herein are measured by mixingsamples of the powders in a medium such as water with a surfactant and ashort exposure to ultrasound through either an ultrasonic bath or horn.The ultrasonic treatment supplies sufficient energy to disperse the softagglomerates into primary spherical particles. The primary particle sizeand size distribution is then measured by light scattering in aMicrotrac instrument. This provides a good measure of the usefuldispersion characteristics of the powder because this simulates thedispersion of the particles in a liquid medium such as a paste or slurrythat is used to deposit the particles in a device, such as a visualdisplay. Thus, the references to particle size herein refer to theprimary particle size, such as after lightly dispersing the softagglomerates of particles.

Further, it is advantageous according to the present invention that theforegoing description of the average size and size distribution of thephosphor particles also applies to the average size and sizedistribution of the intermediate precursor particles that are producedduring the pyrolization step. That is, the size and size distribution ofthe particles changes very little, if at all, during the heat treatmentstep after pyrolization. The morphological properties of the finalphosphor powder are substantially controlled by the properties of theintermediate precursor particles.

The phosphor particles of the present invention are comprised of anumber of crystallites. According to the present invention, the phosphorparticles are highly crystalline and it is preferred that the averagecrystallite size approaches the average particle size such that theparticles are composed of only a few large crystals. The averagecrystallite size of the particles is preferably at least about 25nanometers, more preferably is at least about 40 nanometers, even morepreferably is at least about 60 nanometers and most preferably is atleast about 80 nanometers. In one embodiment, the average crystallitesize is at least about 100 nanometers. As it relates to particle size,the average crystallite size is preferably at least about 10 percent,more preferably at least about 20 percent and most preferably is atleast about 30 percent of the average particle size. Such highlycrystalline phosphors are believed to have increased luminescentefficiency and brightness as compared to phosphor particles havingsmaller crystallites.

The phosphor particles of the present invention advantageously have ahigh degree of purity, that is, a low level of impurities. Impuritiesare those materials that are not intended in the final product. Thus, anactivator ion is not considered an impurity. The level of impurities inthe phosphor powders of the present invention is preferably not greaterthan about 1 atomic percent, more preferably is not greater than about0.1 atomic percent and even more preferably is not greater than about0.01 atomic percent.

The formation of hollow particles is common in spray pyrolysis and canoccur in spray conversion. Hollow phosphor particles may be detrimentalin a number of applications of phosphor powders. In the presentinvention, it has been found that the formation of hollow particles canbe avoided through a combination of the control over pyrolysistemperature, residence time and solution concentration. For example,with constant pyrolysis temperature and residence time, the morphologyof some powders show the presence of progressively more hollow particlesas the solution concentration is raised above 5 weight percent. Thus,the phosphor particles are preferably very dense (not porous) asmeasured by helium pychnometry. Preferably, the particles have aparticle density of at least about 80 percent of the theoreticaldensity, more preferably at least about 90 percent of the theoreticaldensity, and even more preferably at least about 95 percent of thetheoretical density.

The phosphor particles of the present invention are also substantiallyspherical in shape. That is, the particles are not jagged or irregularin shape. Spherical particles are particularly advantageous because theyare able to disperse and coat a device, such as a display panel, moreuniformly with a reduced average thickness. Although the particles aresubstantially spherical, the particles may become faceted as thecrystallite size increases while maintaining a substantially sphericalmorphology.

In addition, the phosphor particles according to the present inventionadvantageously have a low surface area. The particles are substantiallyspherical, which reduces the total surface area for a given mass ofpowder. Further, the elimination of larger particles from the powderbatches eliminates the porosity that is associated with open pores onthe surface of such larger particles. Due to the elimination of thelarge particles, the powder advantageously has a lower surface area.Surface area is typically measured using a BET nitrogen adsorptionmethod which is indicative of the surface area of the powder, includingthe surface area of accessible surface pores on the surface of thepowder. For a given particle size distribution, a lower value of asurface area per unit mass of powder indicates solid or non-porousparticles. Decreased surface area reduces the susceptibility of thephosphor powders to adverse surface reactions, such as degradation frommoisture. This characteristic can advantageously extend the useful lifeof the phosphor powders.

The surfaces of the phosphor particles according to the presentinvention are typically smooth and clean with a minimal deposition ofcontaminants on the particle surface. For example, the outer surfacesare not contaminated with surfactants, as is often the case withparticles produced by liquid precipitation routes. Since the particlesdo not require milling, the particle surfaces do not include majordefects that typically result from milling and can decrease thebrightness of the powders.

In addition, the powder batches of phosphor particles according to thepresent invention are substantially unagglomerated, that is, theyinclude substantially no hard agglomerates or particles. Hardagglomerates are physically coalesced lumps of two or more particlesthat behave as one large particle. Hard agglomerates are disadvantageousin most applications of phosphor powders. It is preferred that no morethan about 1 weight percent of the phosphor particles in the powderbatch of the present invention are in the form of hard agglomerates.More preferably, no more than about 0.5 weight percent of the particlesare in the form of hard agglomerates and even more preferably no morethan about 0.1 weight percent of the particles are in the form of hardagglomerates. In the event that hard agglomerates of the powder do form,they can optionally be broken up, such as by jet-milling the powder.

According to one embodiment of the present invention, the phosphorparticles are composite phosphor particles, wherein the individualparticles include at least a first phosphor phase and at least a secondphase associated with the phosphor phase. The second phase can be adifferent phosphor compound or can be a non-phosphor compound. Suchcomposites can advantageously permit the use of phosphor compounds indevices that would otherwise be unusable. Further, combinations ofdifferent phosphor compounds within one particle can produce emission ofa selected color. The emission of the two phosphor compounds wouldcombine to approximate white light.

According to another embodiment of the present invention, the phosphorparticles are surface modified or coated phosphor particles that includea particulate coating (FIG. 35 d) for non-particulate (film) coating(FIG. 35 a) that substantially encapsulates an outer surface of theparticles. The coating can be a metal, a non-metallic compound or anorganic compound.

Coatings are often desirable to reduce degradation of the phosphorpowder due to moisture or other influences, such as the plasma in aplasma display device. The thin, uniform coatings according to thepresent invention will advantageously permit use of the phosphor powdersunder corrosive conditions. Coatings also create a diffusion barriersuch that activator ions cannot transfer from one particle to another,thereby altering the luminescence characteristics. Coatings can alsocontrol the surface energy levels of the particles.

The coating can be a metal, metal oxide or other inorganic compound suchas a metal sulfide, or can be an organic compound. For example, a metaloxide coating can advantageously be used, such as a metal oxide selectedfrom the group consisting of SiO₂, MgO, Al₂O₃, ZnO, SnO₂ or In₂O₃.Particularly preferred are SiO₂ and Al₂O₃ coatings. Semiconductive oxidecoatings such as SnO₂ or In₂O₃ can be advantageous in some applications.In addition, phosphate coatings, such as zirconium phosphate or aluminumphosphate, can also be advantageous for use in some applications.

The coatings should be relatively thin and uniform. The coating shouldencapsulate the entire particle, but be sufficiently thin such that thecoating doesn't interfere with light transmission. Preferably, thecoating has an average thickness of not greater than about 200nanometers, more preferably not greater than about 100 nanometers, andeven more preferably not greater than about 50 nanometers. The coatingpreferably completely encapsulates the phosphor particle and thereforeshould have an average thickness of at least about 2 nanometers, morepreferably at least about 5 nanometers. In one embodiment, the coatinghas a thickness of from about 2 to 50 nanometers, such as from about 2to 10 nanometers. Further, the particles can include more than onecoating substantially encapsulating the particles to achieve the desiredproperties.

The coating, either particulate or non-particulate, can also include apigment or other material that alters the light characteristics of thephosphor. Red pigments can include compounds such as the iron oxides(Fe₂O₃), cadmium sulfide compounds (CdS) or mercury sulfide compounds(HgS). Green or blue pigments include cobalt oxide (CoO), cobaltaluminate (CoAl₂O₄) or zinc oxide (ZnO). Pigment coatings are capable ofabsorbing selected wavelengths of light leaving the phosphor, therebyacting as a filter to improve the color contrast and purity. Further, adielectric coating, either organic or inorganic, can be used to achievethe appropriate surface charge characteristics to carry out depositionprocesses such as electrostatic deposition.

In addition, the phosphor particles can be coated with an organiccompound such as PMMA (polymethylmethacrylate), polystyrene or similarorganic compounds, including surfactants that aid in the dispersionand/or suspension of the particles in a flowable medium. The organiccoating is preferably not greater than about 100 nanometers thick and issubstantially dense and continuous about particle. The organic coatingscan advantageously prevent corrosion of the phosphor particles,especially in electroluminescent lamps, and also can improve thedispersion characteristics of the particles in a paste or other flowablemedium.

The coating can also be comprised of one or more monolayer coatings,such as from about 1 to 3 monolayer coatings. A monolayer coating isformed by the reaction of an organic or an inorganic molecule with thesurface of the phosphor particles to form a coating layer that isessentially one molecular layer thick. In particular, the formation of amonolayer coating by reaction of the surface of the phosphor powder witha functionalized organo silane such as halo- or amino-silanes, forexample hexamethyldisilazane or trimethylsilylchloride, can be used tomodify and control the hydrophobicity and hydrophilicity of the phosphorpowders. Monolayer coatings of metal oxides (e.g. ZnO or SiO₂) or metalsulfides (e.g. Cu₂S) can be formed as monolayer coatings. Monolayercoatings can allow for greater control over the dispersioncharacteristics of the phosphor powder in a wide variety of pastecompositions and other flowable mediums.

The monolayer coatings may also be applied to phosphor powders that havealready been coated with an organic or inorganic coating, thus providingbetter control over the corrosion characteristics (through the use of athicker coating) as well as dispersibility (through the use of amonolayer coating) of the phosphor powder.

As a direct result of the foregoing powder characteristics, the phosphorpowders of the present invention have many unique and advantageousproperties that are not found in phosphor powders known heretofore.

The phosphor powders of the present invention have a high efficiency,sometimes referred to as quantum efficiency. Efficiency is the overallconversion of excitation energy (electrons or photons) to visiblephotons emitted. According to one embodiment of the present invention,the efficiency of the phosphor powder is at least about 90%. The nearperfect efficiency of the phosphor powders according to the presentinvention is believed to be due to the high crystallinity and homogenousdistribution of activator ion in the host material as well as asubstantially defect-free particle surface.

The phosphor powders also have well-controlled color characteristics,sometimes referred to as emission spectrum characteristics orchromaticity. This important property is due to the ability to preciselycontrol the composition of the host material, the homogenousdistribution of the activator ion and the high purity of the powders.

The phosphor powders also have improved decay time, also referred to aspersistence. Persistence is referred to as the amount of time for thelight emission to decay to 10% of its brightness. Phosphors with longdecay times can result in blurred images when the image moves across thedisplay. The improved decay time of the phosphor powders of the presentinvention is believed to be due primarily to the homogenous distributionof activator ion in the host material.

The phosphor powders also have an improved brightness over prior artphosphor powders. That is, under a given application of energy, thephosphor powders of the present invention produce more light.

Thus, the phosphor powders of the present invention have a uniquecombination of properties that are not found in conventional phosphorpowders. The powders can advantageously be used to form a number ofintermediate products, for example liquid mediums such as pastes orslurries, and can be incorporated into a number of devices, wherein thedevices will have significantly improved performance resulting directlyfrom the characteristics of the photoluminescent phosphor powders of thepresent invention. The devices can include light-emitting lamps anddisplay devices for visually conveying information and graphics. Suchdisplay devices include plasma display panels. Plasma display panels arerelatively thin devices that present graphics and images without the useof a traditional picture tube and operate with modest powerrequirements. Generally, flat panel displays include a phosphor powderselectively dispersed on a viewing panel, wherein the excitation sourcelies behind and in close proximity to the panel.

Plasma displays have image quality that is comparable to current CRTdevices and can be easily scaled to large sizes such as 20 to 60diagonal inches. The displays are bright and lightweight and have athickness of from about 1.5 to 3 inches. A plasma display functions in asimilar manner as fluorescent lighting. In a plasma display, plasmasource, typically a gas mixture, is placed between an opposed array ofaddressable electrodes and a high energy electric field is generatedbetween the electrodes. Upon reaching a critical voltage, a plasma isformed from the gas and UV photons are emitted by the plasma. Colorplasma displays contain three-color photoluminescent phosphor particlesdeposited on the inside of the glass faceplate. The phosphorsselectively emit light when illuminated by the photons. Plasma displaysoperate at relatively low currents and can be driven either by an AC orDC signal. AC plasma systems use a dielectric layer over the electrode,which forms a capacitor. This impedance limits current and provides anecessary charge in the gas mixture.

A cross-section of a plasma display device is illustrated in FIG. 37.The plasma display 1040 comprises two opposed panels 1042 and 1044 inparallel opposed relation. A working gas, typically including xenon, isdisposed and sealed between the two opposing panels 1042 and 1044. Therear panel 1044 includes a backing plate 1046 on which are printed aplurality of electrodes 1048 (cathodes) which are in parallel spacedrelation. An insulator 1050 covers the electrodes and spacers 1052 areutilized to separate the rear panel 1044 from the front panel 1042.

The front panel 1042 includes a glass face plate 1054 which istransparent when observed by the viewer (V). Printed onto the rearsurface of the glass face plate 1054 are a plurality of electrodes 1056(anodes) in parallel spaced relation. An insulator 1058 separates theelectrode from the pixels of phosphor powder 1060. The phosphor powder1060 is typically applied using a thick film paste. When the display1040 is assembled, the electrodes 1048 and 1056 are perpendicular toeach other, forming an XY grid. Thus, each pixel of phosphor powder canbe activated by the addressing an XY coordinate defined by theintersecting electrodes 1048 and 1056.

One of the problems currently encountered in plasma display devices isthe long decay time of the phosphor particles, which creates a “tail” ona moving image. Through control of the phosphor chemistry, suchdecay-related problems can be reduced. Further, the spherical,non-agglomerated nature of the phosphor particles improves theresolution of the plasma display panel.

Plasma display panels typically operate using a xenon gas composition.The Y₂O₃:Eu phosphors of the present invention, doped with from 4 toabout 6 atomic percent Eu, are useful for plasma displays for providingred color. (Y,Gd)BO₃ phosphors including about 14 to 20 atomic percentEu are also useful for red color. Further, the Zn₂ SiO₄:Mn phosphors ofthe present invention, preferably with 0.05 to 2 atomic percent Mn, areuseful for producing a green color. BAM phosphors of the presentinvention are useful for producing a blue color, particularly when dopedwith from about 8 to 12 atomic percent Eu. The phosphors canadvantageously be coated, such as with MgO, to reduce degradation fromthe plasma.

For the plasma display panels, it is important for the phosphor layer tobe as thin and uniform as possible with a minimal number of voids. FIG.38 schematically illustrates a lay down of large agglomerated particlesin a pixel utilizing conventional phosphor powders. The device 1100includes a transparent viewing screen 1102 and a transparent electrodelayer 1104. The phosphor particles 1106 are dispersed in pixels 1108.The phosphor particles are large and agglomerated and result in a numberof voids and unevenness in the surface. This results in decreasedbrightness and decreased image quality.

FIG. 39 illustrates the same device fabricated utilizing phosphorpowders according to the present invention. The device 1110 includestransparent viewing screen 1112 and a transparent electrode 1114. Thephosphor powders 1116 are dispersed in pixels in 1118. The pixels arethinner and more uniform than the conventional pixel. In a preferredembodiment, the phosphor layer constituting the pixel has an averagethickness of not greater than about 3 times the average particle size ofthe powder, preferably not greater than about 2 times the averageparticle size and even more preferably not greater than about 1.5 timesthe average particle size. This unique characteristic is possible due tothe unique combination of small particle size, narrow size distributionand spherical morphology of the phosphor particles. The device willtherefore produce an image having much higher resolution due to theability to form smaller, more uniform pixels and much higher brightnesssince light scattering is significantly reduced and the amount of lightlost due to non-luminescent particles is reduced.

The photoluminescent phosphors of the present invention are also usefulas taggents for security purposes. In this application the phosphors,which are undetectable under normal lighting, become visible uponillumination by a particular energy.

For security purposes, the phosphor particles are dispersed into aliquid vehicle which can be applied onto a surface by standard inkdeposition methods, such as by using an ink jet or a syringe, or byscreen printing. The phosphor particles of the present invention, havinga small size and narrow size distribution, advantageously permit bettercontrol over the printed feature size and complexity. The methodology ofthe present invention also permits unique combinations of phosphorcompounds that are not available using conventional methods. Suchphosphors can be applied to currency, confidential documentation,explosives and munitions, or any other item that may require positiveidentification. The phosphor powders can advantageously be dispersed inan ink which is then used to form indicia on a document or other item,such as a postal envelope.

Useful phosphor compounds for security applications include Y₂O₃:Eu,preferably including 6 to 9 atomic percent Eu. (Y,Gd)BO₃ including 14 to20 atomic percent Eu can also be useful. Such phosphors emit visiblelight upon excitation by an infrared source. The phosphor powders of thepresent invention provide many advantages in such applications. Forexample, the small, monodispersed nature of the particles makes theparticles easy to supply in smaller quantities.

In addition to the foregoing, the phosphors of the present invention canalso be used as target materials for the deposition of phosphorthin-films by electron beam deposition, sputtering and the like. Theparticles can be consolidated to form the target for the process. Thehomogenous concentration of activator ions in the particles will lead tomore uniform and brighter film.

Further, the phosphor particles according to the present invention canbe used for fluorescent lighting elements, including common overheadlighting tubes as well as lamps used to backlight LCD displays, whichare commonly used on laptop computers. Typically, the excitation sourcefor such displays includes mercury vapor.

A fluorescent tubular lighting element is schematically illustrated inFIG. 40. The lighting element 1200 includes a glass tube 1202 that issealed to contain a gas composition, typically including mercury. Theends of the glass tube 1202 include electrodes 1204 and 1206 that ionizethe gas composition thereby stimulating photoluminescent phosphors 1208that are disposed on the inner surface of the glass tube 1202. Themixture of different color phosphors produces a white light, which istypically desired in fluorescent lighting applications.

FIG. 41 schematically illustrates a close-up of the phosphor powders1208 of the present invention on a glass tube 1202. The small andspherical phosphors form a uniform thin layer having a reduced averagethickness, such as less than about 3 times the average particle size ofthe phosphor particles 1208. This uniform and thin surface canadvantageously produce bright, uniform light while consuming less powerthan conventional phosphor powders. It will be appreciated that thelighting element can have a variety of shapes and forms, and often arein the form of very thin tubing for use as an LCD backlight. Such LCDbacklights are particularly applicable to the present invention sincethey require phosphor powders that are small, spherical and have anarrow size distribution so that the powders will readily disperse inthe lighting element.

Preferred phosphor powders for such fluorescent lighting applicationsincluding Y₂O₃:Eu, particularly those including from about 6 to about 9atomic percent Eu. (Y,Gd) BO₃:Eu, including from about 14 to about 20atomic percent Eu, are also useful. Other useful phosphors include Zn₂SiO₄:Mn, particularly from about 0.05 to about 2 atomic percent Mn aswell as BAM:Eu, including from about 6 to about 12 atomic percent Eu.Combinations of the foregoing phosphors can be used to produce a whitelight element. To form these lighting elements, the phosphor particlesare typically dispersed in a liquid vehicle such as a slurry which arethen applied to the interior of a glass tube and dried to form thephosphor layer.

Phosphor powders are typically deposited onto device surfaces orsubstrates by a number of different deposition methods which involve thedirect deposition of the dry powder such as dusting, electrophotographicor electrostatic precipitation, while other deposition methods involveliquid vehicles such as ink jet printing, liquid delivery from asyringe, micro-pens, toner, slurry deposition, paste-based methods andelectrophoresis. In all these deposition methods, the powders describedin the present invention show a number of distinct advantages over thephosphor powders produced by other methods. For example, small,spherical, narrow size distribution phosphor particles are more easilydispersed in liquid vehicles, they remain dispersed for a longer periodand allow printing of smoother and finer features compared to powdermade by alternative methods.

For many of the foregoing applications, phosphor powders are oftendispersed within a paste which is then applied to a surface to obtain aphosphorescent layer. These pastes are commonly used for plasma displaypanels. The powders of the present invention offer many advantages whendispersed in such a paste. For example, the powders will disperse betterthan non-spherical powders of wide size distribution and can thereforeproduce thinner and more uniform layers with a reduced lump count. Sucha thick film paste will produce a brighter display. The packing densityof the phosphors will also be higher. The number of processing steps canalso be advantageously reduced.

One preferred class of intermediate products according to the presentinvention are thick film paste compositions, also referred to as thickfilm inks. These pastes are particularly useful for the application ofthe phosphor particles onto a substrate, such as for use in a flat paneldisplay.

In the thick film process, a viscous paste that includes a functionalparticulate phase, such as phosphor powder, is screen printed onto asubstrate. A porous screen fabricated from stainless steel, polyester,nylon or similar inert material is stretched and attached to a rigidframe. A predetermined pattern is formed on the screen corresponding tothe pattern to be printed. For example, a UV sensitive emulsion can beapplied to the screen and exposed through a positive or negative imageof the design pattern. The screen is then developed to remove portionsof the emulsion in the pattern regions.

The screen is then affixed to a printing device and the thick film pasteis deposited on top of the screen. The substrate to be printed is thenpositioned beneath the screen and the paste is forced through the screenand onto the substrate by a squeegee that traverses the screen. Thus, apattern of traces and/or pads of the paste material is transferred tothe substrate. The substrate with the paste applied in a predeterminedpattern is then subjected to a drying and heating treatment to adherethe functional phase to the substrate. For increased line definition,the applied paste can be further treated, such as through aphotolithographic process, to develop and remove unwanted material fromthe substrate.

Thick film pastes have a complex chemistry and generally include afunctional phase, a binder phase and an organic vehicle phase. Thefunctional phase can include the phosphor powders of the presentinvention which provide a luminescent layer on a substrate. The particlesize, size distribution, surface chemistry and particle shape of theparticles all influence the rheology of the paste.

The binder phase is typically a mixture of inorganic binders such asmetal oxide or glass frit powders. For example, PbO based glasses arecommonly used as binders. The function of the binder phase is to controlthe sintering of the film and assist the adhesion of the functionalphase to the substrate and/or assist in the sintering of the functionalphase. Reactive compounds can also be included in the paste to promoteadherence of the functional phase to the substrate.

Thick film pastes also include an organic vehicle phase that is amixture of solvents, polymers, resins or other organics whose primaryfunction is to provide the appropriate rheology (flow properties) to thepaste. The liquid solvent assists in mixing of the components into ahomogenous paste and substantially evaporates upon application of thepaste to the substrate. Usually the solvent is a volatile liquid such asmethanol, ethanol, terpineol, butyl carbitol, butyl carbitol acetate,aliphatic alcohols, esters, acetone and the like. The other organicvehicle components can include thickeners (sometimes referred to asorganic binders), stabilizing agents, surfactants, wetting agents andthe like. Thickeners provide sufficient viscosity to the paste and alsoacts as a binding agent in the unfired state. Examples of thickenersinclude ethyl cellulose, polyvinyl acetate, resins such as acrylicresin, cellulose resin, polyester, polyamide and the like. Thestabilizing agents reduce oxidation and degradation, stabilize theviscosity or buffer the pH of the paste. For example, triethanolamine isa common stabilizer. Wetting agents and surfactants are well known inthe thick film paste art and can include triethanolamine and phosphateesters.

The different components of the thick film paste are mixed in thedesired proportions in order to produce a substantially homogenous blendwherein the functional phase is well dispersed throughout the paste. Thepowder is often dispersed in the paste and then repeatedly passedthrough a roll-mill to mix the paste. The roll mill can advantageouslybreak-up soft agglomerates of powders in the paste. Typically, the thickfilm paste will include from about 5 to about 95 weight percent, such asfrom about 60 to 80 weight percent, of the functional phase, includingthe phosphor powders of the present invention.

Phosphor paste compositions are disclosed in U.S. Pat. No. 4,724,161,U.S. Pat. No. 4,806,389, U.S. Pat. No. 4,902,567 which are incorporatedherein by reference in their entirety. Generally, phosphors aredeaggregated and are combined with organic additives to form the paste.

Some applications of thick film pastes, such as for forminghigh-resolution display panels, require higher tolerances than can beachieved using standard thick-film technology, as is described above. Asa result, some thick film pastes have photo-imaging capability to enablethe formation of lines and traces with decreased width and pitch. Inthis type of process, a photoactive thick film paste is applied to asubstrate substantially as is described above. The paste can include,for example, a liquid vehicle such as polyvinyl alcohol, that is notcross-linked. The paste is then dried and exposed to ultraviolet lightthrough a photomask to polymerize the exposed portions of paste and thepaste is developed to remove unwanted portions of the paste. Thistechnology permits higher density lines and pixels to be formed. Thecombination of the foregoing technology with the phosphor powders of thepresent invention permits the fabrication of devices with resolution andtolerances as compared to conventional technologies using conventionalphosphor powders.

In addition, a laser can be used instead of ultraviolet light through amask. The laser can be scanned over the surface in a pattern therebyreplacing the need for a mask. The laser light is of sufficiently lowintensity that it does not heating the glass or polymer above itssoftening point. The unirradiated regions of the paste can be removedleaving a pattern.

Likewise, conventional paste technology utilizes heating of a substrateto remove the vehicle from a paste and to fuse particles together ormodify them in some other way. A laser can be used to locally heat thepaste layer and scanned over the paste layer thereby forming a pattern.The laser heating is confined to the paste layer and drives out thepaste vehicle and heats the powder in the paste without appreciablyheating the substrate. This allows heating of particles, delivered usingpastes, without damaging a glass or even polymeric substrate.

Other deposition methods for the phosphor powders can also be used. Forexample, a slurry method can be used to deposit the powder. The powderis typically dispersed in an aqueous slurry including reagents such aspotassium silicate and polyvinyl alcohol, which aids in the adhesion ofthe powder to the surface. For example, the slurry can be poured ontothe substrate and left to settle to the surface. After the phosphorpowder has sedimented onto the substrate the supernatant liquid isdecanted off and the phosphor powder layer is left to dry.

Phosphor particles can also be deposited electrophoretically orelectrostatically. The particles are charged and are brought intocontact with the substrate surface having localized portions of oppositecharge. The layer is typically lacquered to adhere the particles to thesubstrate. Shadow masks can be used to produce the desired pattern onthe substrate surface.

Ink-jet printing is another method for depositing the phosphor powdersin a predetermined pattern. The phosphor powder is dispersed in a liquidmedium and dispensed onto a substrate using an ink jet printing headthat is computer controlled to produce a pattern. The phosphor powdersof the present invention having a small size, narrow size distributionand spherical morphology can be printed into a pattern having a highdensity and high resolution. Other deposition methods utilizing aphosphor powder dispersed in a liquid medium include micro-pen orsyringe deposition, wherein the powders are dispersed and applied to asubstrate using a pen or syringe and are then allowed to dry.

Patterns of phosphors can also be formed by using an ink jet or micropen(small syringe) to dispense sticky material onto a surface in a pattern.Powder is then transferred to the sticky regions. This transfer can bedone is several ways. A sheet covered with powder can be applied to thesurface with the sticky pattern. The powder sticks to the sticky patternand does not stick to the rest of the surface. A nozzle can be used totransfer powder directly to the sticky regions.

Many methods for directly depositing materials onto surfaces requireheating of the particles once deposited to sinter them together anddensify the layer. The densification can be assisted by including amolecular precursor to a material in the liquid containing theparticles. The particle/molecular precursor mixture can be directlywritten onto the surface using ink jet, micropen, and other liquiddispensing methods. This can be followed by heating in a furnace orheating using a localized energy source such as a laser. The heatingconverts the molecular precursor into the functional material containedin the particles thereby filling in the space between the particles withfunctional material.

Thus, the phosphor powders produced according to the present inventionresult in smoother phosphor powder layers when deposited by such liquidor dry powder based deposition methods. Smoother phosphor powder layersare the result of the smaller average particle size, spherical particlemorphology and narrower particle size distribution compared to phosphorpowders produced by other methods. Smoother phosphor powder layers arevaluable in various applications, especially those where the phosphorpowders comprise an imaging device where a high resolution is critical.For example, a smoother phosphor powder layer in a display applicationwhere the phosphor layer produces light that is photographed results inimproved definition and distinction of the photographed image.

A variety of deposition techniques often degrade the properties of thepowders, especially brightness. An example is the three roll millingused to form pastes that are photoprinted, screen printed, directlywritten with a microsyringe and others. A method for increasing thebrightness of the phosphor particles once deposited on the surface is toirradiate them with a laser (Argon ion, krypton ion, YAG, excimer, etc.. . ). The laser light increases the temperature of the particlesthereby annealing them and increasing the brightness. The laser heatingof the particles can be carried out for particles on glass or evenpolymeric substrates since the laser causes local heating of theparticles without heating the glass above its softening point. Thisapproach is useful for phosphors.

The phosphor particle layer deposited onto a surface often needs to becoated to protect the layer from plasmas, moisture, electrons, photons,etc. Coatings can be formed by sputtering, but this requires a mask toavoid deposition onto undesired areas of the substrate. Laser-inducedchemical vapor deposition (LCVD) of metal oxides and other materialsonto particles can allow localized deposition of material to coatphosphor particles without coating other areas. The laser heating of theparticles that drives the CVD can be carried out for particles on glassor even polymeric substrates because the laser causes local heating ofthe particles without heating the glass or polymer above its softeningpoint.

EXAMPLES

The following examples demonstrate the advantages of the BAM phosphorpowders according to the present invention and the method for making thepowders.

1. BAM Precursor Selection

Using aluminum nitrate hydrate (Al(NO₃)₃.9H₂O), a 5 weight percentsolution was made based on Ba_(0.95)Eu_(0.05)MgAl₁₀O₁₇ (i.e. 5 atomicpercent europium as a dopant). Stirring the solution resulted in acrystalline deposition of barium nitrate. Four equivalents of ethyleneglycol were added as a chelating agent to increase the solubility of thebarium nitrate, however the deposit still remained.

Similar solutions containing aluminum nitrate and having a totalprecursor concentration of 5, 7.5 and 10 weight percent were prepared.Polyether was added as a second chelating agent to increase thesolubility of the barium nitrate. The results are listed in Table III.

TABLE III Example Weight Percent Solution Result BAM-1 5.0 Mostly insolution BAM-2 7.5 Slight suspension of solid BAM-3 10.0 Difficult toput into solution

The solutions from Examples BAM-1 & BAM-2 were nebulized using anultrasonic generator at a frequency of about 1.6 MHz and carried througha furnace at 750° C., substantially as described herein. Both atomizedpoorly (low production rate), although some powder was collected fromExample BAM-1. The collected powder had a brown/black appearance.Heating the powder to 1350° C. under flowing forming gas (7% H₂/93% N₂)produced a grey powder that x-ray diffraction indicated was phase pure.Further heat treatment in air at 1350° C. for 2 hours produced a white,phase pure powder.

Nonetheless, it was concluded that aluminum nitrate as a precursor wasnot a viable alternative due to solubility problems associated withbarium nitrate.

2. BAM Process Temperature

Based on the foregoing, fumed particulate alumina was selected as aprecursor component. Europium nitrate, barium nitrate and magnesiumnitrate were used as the remaining precursors, for a total precursorconcentration of 7.5 weight percent based on the final BAM composition.The solution was nebulized using ultrasonic transducers at a frequencyof about 1.6 MHZ to form an aerosol. The aerosol was carried through atubular furnace at varying temperatures, as indicated in Table IV.

TABLE IV Crystalline Conversion Phases after Heat Example TemperatureCrystalline Phases Treatment BAM-4 600° C. Ba(NO₃)₂ BaAl₂O₄, BAM BAM-5700° C. Ba(NO₃)₂ BaAl₂O₄, BAM BAM-6 800° C. Amorphous BaAl₂O₄, BAM BAM-7900° C. Mainly amorphous BaAl₂O₄, BAM Some BaOBelow 700° C. the barium nitrate did not fully decompose. It wasconcluded that a preferred range for producing a spray-convertedintermediate product was at least about 700° C. and preferably 800° C.to 900° C.

A sample of each of the spray-converted intermediate powders was heattreated at 1500° C. for 2 hours under a forming gas of 10% H₂/90% N₂ anda sample of each powder was heat treated at 1400° C. for 1 hour in air.Each post treatment resulted in a powder that was not phase pure(BaAl₂O₄ impurity) and there was virtually no difference in the x-raydiffraction patterns for the powders treated in forming gas versus thepowders treated in air.

3. BAM Precursor Concentration

In an effort to eliminate the aluminate impurity identified above, themetal stoichiometry in the precursor solution was varied. The solutionsand results of processing are summarized in Table V. All solutions wereformed into an aerosol using ultrasonic atomizers at a frequency ofabout 1.6 MHz and were spray converted at a temperature of 750□C in atubular furnace.

TABLE V Weight Loss Heat during Crystalline Relative Precursor TreatmentHeat Phases of PL Example Stoichiometry Atmosphere Treatment FinalPowder Intensity BAM-8 Ba_(0.95)Eu_(0.05)Mg_(1.5)Al₁₀ H₂/N₂ 10.4%BaAl₂O₄ 13 O_(x) BAM-9 B_(0.95)Eu_(0.05)Mg_(1.75) H₂/N₂ 8.5% BaAl₂O₄ 18Al₁₀O_(x) BAM-10 Ba_(0.95)Eu_(0.05)Mg_(2.0) H₂/N₂ 8.2% BaAl₂O₄ 7Al₁₀O_(x) BAM-11 Ba_(0.95)Eu_(0.05)MgAl₁₂ H₂/N₂ 7.8% BaAl₂O₄ + 42 O_(x)BAM BAM-12 Ba_(0.95)Eu_(0.05)MgAl₁₄ H₂/N₂ 7.2% BAM 37 O_(x) BAM-13Ba_(0.95)Eu_(0.05)MgAl₁₆ H₂/N₂ 5.9% BAM 29 O_(x) BAM-14Ba_(0.95)Eu_(0.05)MgAl₂₀ H₂/N₂ 4.5% BAM 14 O_(x) BAM-15Ba_(0.95)Eu_(0.05)Mg_(0.89) Air 12.0% BaAl₂O₄ + — Al₁₃O_(x) BAM BAM-16Ba_(0.95)Eu_(0.05)Mg_(1.11) Air 13.6% BaAl₂O₄ + — Al₁₃O_(x) BAM BAM-17Ba_(0.95)Eu_(0.05)MgAl₁₃ Air 7.9% BaAl₂O₄ + — O_(x) BAM BAM-18Ba_(0.95)Eu_(0.05)MgAl₁₂ Air 7.0% BaAl₂O₄ + — O_(x) BAM BAM-19Ba_(0.95)Eu_(0.05)MgAl₁₄ Air 7.0% BAM — O_(x)

Increasing the magnesium content in Examples BAM-8, 9 and 10 did notlead to a decrease of the barium aluminate phase. However, when thealuminum content was increased keeping the barium and magnesium ratiofixed, phase pure BAM was produced. Therefore, it was concluded that anexcess of aluminum in the precursor, such as 40% or more excess, isdesirable for producing phase pure BAM.

The photoluminescence (PL) data indicates that the maximum intensityoccurs for powders treated in a reducing atmosphere, likely due to thereduction of europium to the Eu²⁺ state.

Based on the foregoing examples, BAM powder was produced as follows.Barium nitrate, europium nitrate, magnesium nitrate and colloidalalumina were formed into a precursor solution having a concentration ofabout 8 weight percent based on the equivalent of BAM. Europium wasincorporated at 5 atomic percent. The solution was atomized usingultrasonic transducers at a frequency of about 1.6 MHz. The aerosol waspyrolyzed in a tubular furnace at a reaction temperature of 950° C. toform a spray-converted intermediate precursor powder. The powder wasthen heat-treated at 1450° C. for 2 hours under an atmosphere of H₂/N₂.This powder is illustrated the photomicrograph of FIG. 42. The particlesize distribution of the powder is illustrated in FIG. 43. The averageparticle size was 1.88 μm and 90% of the particles by weight were lessthan 3.51 pm in size. The powder exhibited strong photoluminescencecharacteristics.

As a further example, a yttria powder batch was produced according tothe present invention. An aqueous precursor solution was formedcomprising yttrium nitrate and europium nitrate in a ratio to yield aphosphor comprising Y₂O₃ and 8.6 atomic percent Eu. The total precursorconcentration was 7.5 weight percent based on the final product.

The liquid solution was atomized using ultrasonic transducers at afrequency of 1.6 MHz. Air was used as a carrier gas and the aerosol wascarried through a tubular furnace having a temperature of 800° C. Thetotal residence time in the furnace was about 1-2 seconds. Thepyrolyzation at 800° C. resulted in intermediate precursor particles ofa low crystallinity yttrium compound.

The intermediate precursor particles were then heated in batch mode at atemperature of 1400° C. for 60 minutes in air. The heating ramp rate was10° C./minute.

The resulting powder is illustrated in the SEM photomicrograph of FIG.44. The particle size distribution is illustrated in FIG. 45. Theaverage particle size was 2.476 μm and 90 percent of the particles had asize of less than 4.150 μm. The x-ray diffraction pattern illustrated inFIG. 46 shows that the particles are substantially phase pure Y₂O₃.

A yttrium gadolinium borate powder batch was also produced according tothe present invention. An aqueous precursor solution was formedcomprising yttrium nitrate, gadolinium nitrate, europium nitrate andboric acid in a ratio to yield a (Y,Gd)BO₃ phosphor having a Y:Gd ratioof 3 and an Eu concentration of 16 atomic percent. The total precursorconcentration was 8.0 weight percent based on the final product.

The liquid solution was atomized using ultrasonic transducers at afrequency of 1.6 MHz. Air was used as a carrier gas and the aerosol wascarried through a tubular furnace having a temperature of 950° C. Thetotal residence time in the furnace was about 1-2 seconds. Thepyrolyzation at 950° C. resulted in intermediate precursor particleshaving low crystallinity.

The intermediate precursor particles were then heated in batch mode at atemperature of 1150° C. for 60 minutes in air. The heating ramp rate was10° C./minute.

The resulting powder is illustrated in the SEM photomicrograph of FIG.47. The particle size distribution is illustrated in FIG. 48. Theaverage particle size was 2.139 μm and 90 percent of the particles had asize of less than 3.608 μm. The x-ray diffraction pattern illustrated inFIG. 49 shows that the particles are substantially phase pure yttriumborate and gadolinium borate having a high crystallinity.

In another example, a zinc silicate powder batch was produced accordingto the present invention. A precursor solution was formed comprisingzinc nitrate and manganese nitrate along with colloidal silica (CabotL-90, Cabot Corporation, Boyertown, Pa.). An excess of 50 molar percentsilica was used in the precursor liquid and the concentration ofmanganese was 5 atomic percent. The total precursor concentration wasabout 7.5 weight percent based on the final product. The liquid solutionwas atomized using ultrasonic transducers at a frequency of 1.6 MHz. Airwas used as a carrier gas and the aerosol was carried through a tubularfurnace having a temperature of 900° C. The total residence time in thefurnace was about 1-2 seconds. The pyrolyzation at 900° C. resulted inintermediate precursor particles having a low crystallinity.

The intermediate precursor particles were then heated in batch mode at atemperature of 1175° C. for 60 minutes in air. The heating ramp rate was10° C./minute.

The resulting powder is illustrated in the SEM photomicrograph of FIG.50. The particle size distribution is illustrated in FIG. 51. Theaverage particle size was 2.533 μm and 90 percent of the particles had asize of less than 4.467 μm. The x-ray diffraction pattern illustrated inFIG. 52 shows that the particles are substantially phase pure Zn₂SiO₄.

While various embodiments of the present invention have been describedin detail, it is apparent that modifications and adaptations of thoseembodiments will occur to those skilled in the art. However, it is to beexpressly understood that such modifications and adaptations are withinthe spirit and scope of the present invention.

1. A security feature comprising oxygen-containing phosphor particlesprinted onto the surface of an article to form an identifiable mark onthe article, wherein said phosphor particles have a substantiallyspherical morphology and have a weight average particle size of notgreater than about 10 μm, and wherein said phosphor particles comprise(Y,Gd)BO₃.
 2. The security feature of claim 1, wherein the phosphorparticles have an average particle size of at least about 0.1 μm and notgreater than about 10 μm.
 3. The security feature of claim 1, whereinthe phosphor particles have an average particle size of not greater thanabout 5 μm.
 4. The security feature of claim 1, wherein the phosphorparticles have an average particle size of not greater than about 3 μm.5. The security feature of claim 1, wherein the phosphor particles havean average particle size of from about 0.3 μm to about 5 μm.
 6. Thesecurity feature of claim 1, wherein at least about 80 weight percent ofsaid particles are not larger than two times said average particle size.7. The security feature of claim 1, wherein the security featurecomprises an ink-jet printed identifiable mark.
 8. The security featureof claim 1, wherein the security feature comprises a syringe printedidentifiable mark.
 9. The security feature of claim 1, wherein thesecurity feature comprises a screen printed identifiable mark.
 10. Thesecurity feature of claim 1, wherein the security feature emits visiblelight upon excitation by an infrared source.
 11. The security feature ofclaim 1, wherein the phosphor particles can be excited by an infraredsource.
 12. A process for forming a security feature printed onto asubstrate, comprising: printing an ink onto a substrate to form thesecurity feature, wherein the ink comprises oxygen-containing phosphorparticles and a vehicle, said phosphor particles having a weight averageparticle size of not greater than about 10 μm and a substantiallyspherical morphology, and wherein at least about 80 weight percent ofsaid particles are not larger than two times said average particle sizeand wherein the oxygen-containing phosphor particles comprise a compoundselected from the group consisting of (Y,Gd)BO₃ and Y₂O₃:Eu.
 13. Theprocess of claim 12, wherein the phosphor particles have an averageparticle size of at least about 0.1 μm and not greater than about 10 μm.14. The process of claim 12, wherein the phosphor particles have anaverage particle size of not greater than about 5 μm.
 15. The process ofclaim 12, wherein the phosphor particles have an average particle sizeof not greater than about 3 μm.
 16. The process of claim 12, wherein thephosphor particles have an average particle size of from about 0.3 μm toabout 5 μm.
 17. The process of claim 12, wherein the phosphor particlescomprise Y₂O₃:Eu.
 18. The process of claim 12, wherein the printingcomprises ink jet printing.
 19. The process of claim 12, wherein theprinting comprises syringe printing.
 20. The process of claim 12,wherein the printing comprises screen printing.
 21. The process of claim12, wherein the security feature emits visible light upon excitation byan infrared source.
 22. The process of claim 12, wherein the phosphorparticles can be excited by an infrared source.
 23. The process of claim12, wherein the substrate comprises currency.
 24. The process of claim12, wherein the substrate comprises a confidential document.
 25. Theprocess of claim 12, wherein the substrate comprises explosives ormunitions.
 26. A process for forming a security feature printed onto asubstrate, comprising: printing an ink onto a substrate to form thesecurity feature, wherein the ink comprises photoluminescentsubstantially spherical phosphor particles and a vehicle, wherein saidphosphor particles comprise (Y,Gd)BO₃ and have a weight average particlesize of not greater than about 10 μm.
 27. The process of claim 26,wherein the phosphor particles have an average particle size of at leastabout 0.1 μm and not greater than about 10 μm.
 28. The process of claim26, wherein the phosphor particles have an average particle size of notgreater than about 5 μm.
 29. The process of claim 26, wherein thephosphor particles have an average particle size of not greater thanabout 3 μm.
 30. The process of claim 26, wherein the phosphor particleshave an average particle size of from about 0.3 μm to about 5 μm. 31.The process of claim 26, wherein at least about 80 weight percent ofsaid particles are not larger than two times said average particle size.32. The process of claim 26, wherein the printing comprises ink jetprinting.
 33. The process of claim 26, wherein the printing comprisessyringe printing.
 34. The process of claim 26, wherein the printingcomprises screen printing.
 35. The process of claim 26, wherein thesecurity feature emits visible light upon excitation by an infraredsource.
 36. The process of claim 26, wherein the phosphor particles canbe excited by an infrared source.
 37. The process of claim 26, whereinthe substrate comprises currency.
 38. The process of claim 26, whereinthe substrate comprises a confidential document.
 39. The process ofclaim 26, wherein the substrate comprises explosives or munitions.
 40. Asecurity feature comprising photoluminescent substantially sphericalphosphor particles printed onto the surface of an article to form anidentifiable mark on the article, wherein said phosphor particles have aweight average particle size of not greater than about 10 μm, wherein atleast about 80 weight percent of said particles are not larger than twotimes said average particle size and where the security feature emitsvisible light upon excitation by an infrared source, wherein saidphosphor particles comprise a compound selected from the groupconsisting of (Y,Gd)BO₃ and Y₂O₃:Eu.
 41. A security feature as recitedin claim 1, wherein the security feature is printed on currency.
 42. Asecurity feature as recited in claim 1, wherein the security feature isprinted on confidential documentation.
 43. A security feature as recitedin claim 1, wherein the security feature is printed on explosives orammunitions.
 44. A security feature as recited in claim 40, wherein saidphosphor particles have a weight average particle size of at least about0.1 μm and not greater than about 10μm.
 45. A security feature asrecited in claim 44, wherein said phosphor particles have a weightaverage particle size of not greater than about 5 μm.
 46. A securityfeature as recited in claim 40, wherein said phosphor particles compriseY₂O₃:Eu.